摘要:

11 Cu Ag Au; Zn Cd Hg By J. SILVER Department of Chemistry University of Essex Colchester C04 3SQ 1 Copper Silver and Gold Copper.-An extremely useful review with 385 references on copper chemistry covering the year 198 1 has appeared. ’ Copper(1).The phase diagrams CuC1-MC1 (M = Cd La or Yb) were studied by d.t.aV2 Tetrabutylammonium dichlorocuprate and dibromocuprate contain anions that are linear. Studies on the thermodynamics of cuprous halide complex formation in acetonitrile have established that the stability decreases in the order C1- > Br-> I-.4 The diamagnetic adducts [CuX(py)],.quinone (X = C1 or Br) are said to be olefin complexes.’ CuXL (X = C1 Br or I; L = 2-amino-1,3,4-thiadiazoleor 2-ethylamino- 1,3,4-thiadiazole) have been studied by conductimetric methods and i.r.spectroscopy.6 63Cu and 65Cu n.q.r. spectra of CuCl and CuBr complexes of imi- dazolidine-2-thione and tetrahydro- 1H-pyrimidine-2-thione have been rep~rted.~ Bromo(tri-t-butylphosphine)copper(I) tetramer contains a cubane-type Cu4Br core.* The structures of 1 1 complexes of Cu’I with 2-methylpyridine (A) 2,2,6,6- tetramethylpiperidine (B) and acridine (C) were studied a cubane-type unit [Cu4I,(2Me-py),] was found in A B is a di-p-iodo bridged dimer [Cu2Iz(tmpip),] and C is a ‘split stair’ polymer (-CUL-I-),.~ Structures of five complexes CuIL (L = 2-methylpyridine 2-ethylpyridine quinoline 3,5-dimethylpyridine or 2,6-dimethylpyridine) have been reported. The first four complexes contain Cu atoms pseudotetrahedrally co-ordinated to two N atoms one from each base and two bridging iodine atoms; in the fifth complex the Cu atom is three co-ordinate.” The complexes [RO,P],CuCl (R = Et or Me) and CuC1(RN=PPh3) {where R = P(0) (OPh),} have been characterized.’ ’ Spectrophotometric studies have been reported on the reactions of the phenolic oxidative coupling initiator py4Cu4C1402 and of B.J. Hathaway Coord. Chem. Rev. 1983 52 87. ’I R. Blachnik and Enninga Z. Anorg. Allg. Chem. 1983 503,133. M. Asplund S. Jagner and M. Nilsson Acta Chem. Scand. Ser. A 1983 37,57. S. Ahrland K. Nilsson and B. Tagesson Acta Chem. Scand. Ser. A 1983 37,193. ’ E. Balogh-Hergovich and G. Speier Inorg. Chim. Acta 1983 74,61. A.C. Fabretti G. Peyronel A. Giusti and A. F. Zanoli Polyhedron 1983 2 475.’ J.-M. Bret P. Castan G. Jugie A. Dubourg and R. Roques J. Chem. SOC.,Dalton Trans. 1983 301. R. G. Goel and A. L. Beauchamp Inorg. Chem. 1983 22 395. P. C. Healy C. Pakawatchai C. L. Raston B. W. Skelton and A. H. White J. Chem. SOC. Dalton Trans. 1983 1905. lo P. C. Healy C. Pakawatchai and A. H. White J. Chem. SOC. Dalton Trans. 1983 1917. I’ (a) J. C. Bommer and K. W. Morse Inorg. Chem. 1983 22 592; (b) K. Bartel K. V. Werner and W. Beck J. Organomet. Chem. 1983 243,79. 275 276 J. Silver py4cU4c160 with pyridine.' The cation-radical salt of tetraselenotetracene with the dibromocuprate anion contains CuBr2-anions that have a distorted linear configuration.l3 Bis{ p-chloro-[ N,N'-ethanediylidenebis(1-isopropyl-2-methylpropylamine)]copper(1)} is an unsymmetrically Cl-bridged dimer.' [Ph4P]3[MoOS3(CuC1)3][CuC12] contains a tris[chlorocopper(~)]-oxotrithio-molybdate(vI)2- anion co-crystallizing with a linear [CuCl,]- anion.l5 The vapour deposition of CuO by Cl, HgCl, and 1 transport agents has been studied.I6 CsCuO has been prepared." Cs3Cu504 Rb2KCu504 RbK2Cu504 and K3Cu504 are reported.18 The heterogeneous decomposition of propan-2-01 vapour in the presence of CuO has been induced by i.r.laser radiation." Charge-density distribution in crystals of CuA10 with d-s hybridization has been investigated.,' Mass spectrometric studies of the decomposition and the heat of formation of CuInS have been presented.,' CuGaSe and CuGaTe have been studied., The crystal structure of TiCu,P shows it belongs to the Cu2Sb structure family.23 The structure of tetrabutylammonium dicyanocuprate( I) contains a [Cu(CN),]- chain., Preliminary results of the direct electron transfer rate of Cu+-Mo(CN);- ion-pairs generated by IT excitation of Cu2+-Mo(CN);- association are reported.25 The thermal behaviour of CuSO and Cu,OSO and crystal formation was studied.16 The cubane-like structure of a tetranuclear Cu' carbonyl complex [Cu(q)(CO)] (q = 2-methylquinolin-8-olate) forms in tetrahydrofuran under a pressure of 60 atm of CO at 65 0C.26 The crystal structure of Cu(CO)EtSO shows a Cu atom in nearly tetrahedral ge~metry.~' CO adducts of the Cu' derivatives of the new ligands bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl]X (X = amine ether or sulphide) are repor- ted.,* [CuCO(O-t-Bu)] has a CU404 core of cubane form.29 The synthesis has been reported of a series of monolefin complexes containing distorted tetrahedral CU'.~' Evidence for Cu(C&) is found in e.s.r.spectra at 77 K.31 Mesitylcopper(r) (CuMes) was shown to be a cyclic pentameric aryl copper complex in the solid and to undergo ring contraction with tetrahydrothiophene to give [CU,M~S,(C,H~S)~].~~ The struc- l2 G. Davies M. A. El-Sayed and A. E. Fasano Inorg. Chim. Acta 1983 71 95. l3 R. P. Shibaeva V. F. Kaminskii E. B. Yagubski and L. A. Kushch Sou. Phys.-Crystallogr. (Engl. Transl.) 1983 28 48. 14 H. T. Dieck and L. Stamp Acta Crystallogr. 1983 C39 841. l5 W. Clegg G. D. Garner J. R. Nicholson and P. R. Raithby Acta Crystallogr. 1983 C39 1007.l6 L. Bald M. Spiess R. Gruehn and T. Kohlmann Z. Anorg. Allg. Chem. 1983 498 153. H. Klassen and R. Hoppe Z. Anorg. Allg. Chem. 1983 497 70. R. Hoppe and W. Losert Z. Anorg. Allg. Chem. 1983 504 60. " W. D. Farneth P. G. Zimmerman D. J. Hogenkamp and S. D. Kennedy J. Am. Chem. SOC.,1983,105 1126. 20 T. Ishiguro N. Ishizawa N. Mizutani M. Kato K. Tanaka and F. Marumo Acta Crystallogr. 1983 B39 564. 21 H. Wiedemeier and R. Santandrea Z. Anorg. Allg. Chem. 1983 497 105. 22 A. Kraft G. Kiihn and W. Moiler Z. Anorg. Allg. Chem. 1983 504 155. 23 W. Carillo-Cabrera Acta Chem. Scand. Ser. A 1983 37 93. 24 M. Asplund S. Jagner and M. Nilsson Acta Chem. Scand. Ser. A 1983 37 165. 25 H. Hennig A. Rehorek D. Rehorek P. L. Thomas and D. Bazold Inorg.Chim. Acta 1983 77 LII. 26 M. Pasquali R. Faischi C. Floriani and P. F. Zanazzi J. Chem. SOC.,Chem. Commun. 1983 613. 27 G. Doyle K. A. Eriksen and D. Van Engen Inorg. Chem. 1983 22 2892. 28 T. N. Sorrel1 and M. R. Malachowski Inorg. Chem. 1983 22 1883. 29 R. L. Geerts J. C. Huffman K. Folting T. H. Lemmen and K. G. Caulton J. Am. Chem. SOC.,1983 105 3503. 30 J. S. Thompson R. L. Harlow and J. F. Whitney J. Am. Chem. Soc. 1983 105 3522. 31 A. J. Buck B. Mile and J. A. Howard J. Am. Chem. SOC.,1983 105 3381. 32 S. Gambarotta. C. Floriani A. Chiesi-Villa and C. Guastini J. Chem. SOC.,Chem. Commun. 1983 1156. Cu,Ag Au; Zn,Cd Hg 277 ture of tetrakis(is0cyanide)-bis( p-phenoxo)dicopper(I) has been described; two phenoxo and two isocyanide ligands are bound to each CU.~ (PEt3),CuBPh and (PPh3),CuBPh4 react with CS2 generating [(PEf3),-Cu( S2CPEt3)]BPh4 and (PP~,),CU(S~CP~).~~ In [(PPh3),Cu( S2CPEt3)]BPh4 the Cu ion is in four co-ordination to two S atoms and two triphenylphosphine groups.34 In [(PPh,),Cu( p-S,CSCH,SCS,)Cu( PPh,),] the bridging ligand is formed from a double head-to-tail condensation of three CS2 molecule^.^^ CS with arylcopper( I) complexes and bis(dipheny1phosphino)methane (dppm) in toluene affords [Cu,(dppm),(CS,),] this consists of a square arrangement of Cu atoms.36 The complexes of [(PhS)CuS2MoS2I2- and [(PhS)CuS2MoS2Cu(SPh)I2-have trigonal planar Cu co-~rdinations.~~ is a thiaether complex [CU~(C~~H~,N,S,)]~+ containing a meta-xylyl dinucleating agent ;both Cu atoms have distorted tetrahedral ge~metries.~~ Isomers of the mixed bimetal complex (t-BuNC),Mo( p-t-B~s)~CuBr have been reported to contain Cu in almost ideal trigonal planar geometry." The structure of (triphos)Cu(O,CH) (triphos = 1,11-tris(diphenylphosphinomethy1)-ethane) and its reactions with C02 CS, and COS has been studied.,' The reaction of mesitylcopper(1) (CrAr) with 172-bis(diphenylphosphino)ethane (dppe) gives [(dppe),Cu2Ar2] which consists of a linear [CuArJ unit with a tetrahedral [Cu(dppe),]+ counter ion.,' The structures of bis(tetramethylammonium)hexa(thiol-ato)tetracuprate(I) polymorphs are reported.42 The formation of 176-bis( N-methyl- benzimidazol-2-yl)-2,5-dithiahexanecopper( I) perchlorate from the CU" compound by photoinduced reduction in dimethylformamide has been reported.43 In tris[2( 1H)-pyridinethione-S]copper(~)nitrate each Cu atom is surrounded by three S atoms in a planar configuration.44 The structure of [2-(Me,Si)2C(Cu)C5H,N]2 contains a Cu-Cu interaction of 2.412( 1) A.45The distorted tetrahedral Cu' structures of [Cu(btz),][PPh] and [C~,(bt),][C10,]~ (btz = 2,2'-bi-4,5-dihydrothiazineand bt = 2,2'-bi-2-thiazoline) have been The photophysical properties of a series of com-plexes of the type Cu(NN),+ {where the (NN) ligands are 2,9-dimethyl-l,10-phenanthroline 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline and 4,4',6,6'-tetramethyl-2,2'-bipyridine) were characteri~ed.~~Cu(pze)BF {pze = bis-[2-(3$dimethyl-1-pyrazolylethyl]ether} contains a three co-ordinate Cu' ion.,* 33 M.Pasquali P.Faischi C. Floriani and A. Gaetani-Manfredotti J. Chem. SOC.,Chem. Commun. 1983 197. 34 C. Bianchini C. A. Ghilardi A. Meli and A. Orlandini Inorg. Chem. 1983 22 2188. 35 C. Bianchini C. A. Ghilardi A. Meli S. Midollini and A. Orlandini J. Chem. SOC.,Chem. Commun. 1983 545. 36 A. M. M. Lanfredi A. Tiripicchio A. Camus and N. Matsich J. Chem. Soc. Chem. Commun. 1983,1126. 37 S. R. Acott C. D. Garner J. R. Nicholson and W. Clegg J. Chem. SOC.,Dalton Trans. 1983 713. 38 K. D. Karlin J. C. Hayes J. P. Hutchinson and J. Zubieta Inorg. Chim. Acta 1983 78 L45. 39 N. C. Payne N. Okura and S. Otsuka J. Am. Chem. SOC.,1983 105 245. 40 C. Bianchini C. A. Ghilardi A. Meli S. Midollini and A. Orlandini J. Organornet. Chem.1983 248 C13. 41 P. Leoni M. Pasquali and C. A. Ghilardi J. Chem. SOC.,Chem. Commun. 1983 240. 42 I. G. Dance G. A. Bowmaker G. R. Clark and J. K. Seadon Polyhedron 1983 2 1031. 43 P. L. Verheijdt J. G. Haasnoot and J. Reedijk Inorg. Chim. Acra 1983 76 L43. 44 S. C. Kokkou S. Fortier P. J. Rentzeperis and P. Karagiannidis Acra Crystallogr. 1983 C39 178. 45 R. 1. Papasergio C. L. Raston and A. H. White J. Chem. SOC.,Chem. Commun. 1983 1419. 46 M. G. B. Drew T. R. Pearson B. Murphy and S. M. Nelson Polyhedron 1983 2 269. 47 J. R. Kirchhoff R. E. Gamache jun. M. W. Blaskie A. A. Del Paggio R. K. Lengel and D. R. McMillin Inorg. Chem. 1983 22 2380. 278 J Silver Resonance Raman spectra of a series of Cu' complexes of a-di-imine ligands have been inter~reted.,~Bis(tripheny1phosphine)pyridine and pyrazine-carboxy-latecopper(I) complexes have been shown to contain Cu' tetrahedrally co-ordinated to two molecules of triphenylphosphine to a N atom and a carboxylate group." A mechanistic investigation of Cu-catalysed reactions of diphenyliodinium salts has identified Cu' as the catalytically active species.50 Dioxygen activation by photoexcited copper atoms has been reported the bonding in Cu(0,) is between Cu+ and 0,ions with the odd electron residing mainly on the dioxygen m~iety.~' Second-order rate constants have been determined for the oxidation of Cu(aq)' by various Ru"' complexes in perchlorate solutions at 25 "C and 1.O M ionic strength.52 The photoaddition of alkyl halides to olefins catalysed by Cu' complexes has been Allenylcopper( I) species add to N-sulphinylaniline to give N-phenyl 2-a1 kynyls~lphinamides.~~ Copper(11).Structural and thermodynamic aspects of the phase transition in CU~,,~Z~~,, A number of CSCUM''1F6 complexes SiF6.6H20 have been rep~rted.'~ were studied.j6 Tetragonal distortions and vibronic coupling in CuF2- complexes have been described.57 Cu" chloride complex equilibrium constants have been determined58 and stability constants of Cu(OAc)Cl CuCI, CuCuC13 and LiCuC1 in acetic acid solution calc~lated.'~ Evidence that CuCl+ is the reactive species in the chlorination of cyclohexene by CuC12 has been presented.60 A series of bis(dithiocarbamat0)di-p-chloro(xx) complexes have been synthe- sized.61 The crystal structure of C~F,(3-methyl-5-phenylpyrazole)~( BF4)2 contains dimeric co-square planar cations.62 [Cu(C,H NO)2C12)2,63 [Cu( N,N,N'-triethyl-ethylenediamine)2C1,]264 and [CuCI(C,H,N)(OMe)] 65 contain chloro-bridge$ Cul'dimers.Di-p-chloro-bis[chloro(l,2-cyclohexanedionedioxime-N,~')copper(11) contains Cu in a distorted square pyramid monomer linked as dimers by two chloro-bridges.66 The structures of [CuLC12] and CuL2(OH),.2H,O (L = 2,3-pyrazinedicarboxamide) were determined the former is a dimer containing two bridging chlorines and the latter is a monomeric complex.67 48 P. Leupin and C. W. Schlapfer 1.Chem. Soc. Dalton Trans. 1983 1635. 49 F. Cariati L. Naldini A. Panzanelli F. Demartin and M. Manassero fnorg. Chim. Acta 1983 69 117.50 T. P. Lockhart J. Am. Chem. Soc. 1983 105 1940. 5' G. A. Ozin S. A. Mitchell and J. Garcia-Prieto J. Am. Chem. Soc. 1983 105 6399. 52 K. M. Davies fnorg. Chem. 1983 22 615. 53 M. Mitani I. Kato and K. Koyama J. Am. Chem. Soc. 1983 105 6719. 54 K. Ruitenberg and P. Vermeer J. Organomet. Chem. 1983 256 175. 5s B. Ya. Sukharevskii E. 0.Tsybul'skii G. E. Statalova and I. M. Vitebskii Soo. Phyx-Crystallogr. (Engl. Trans/.),1983 28 288. 56 D. Babel and F. Binder 2. Inorg. Allg. Chem. 1983 505 153. 57 R. Bbca P. Pelikan M. Breza and J. Gaz6 Polyhedron 1983 2 921. 58 R. W. Ramette and G. Fan Inorg. Chem. 1983 22 3323. 59 M. A. Khan J. Meullemeestre M. J. Schwing and F. Vierling Polyhedron 1983 2 459. 60 P. H.Gamlen M. S. Henty and H. L. Roberts J. Chem. Soc. Dalton Trans. 1983 1373. 61 K. K. M. Yusuff K. Muhammad Bashees and M. Gopalan Polyhedron 1983 2 839. 62 W. C. Velthuizen J. G. Haasnoot A. J. Kinneging F. J. Rietmeijer and J. Reedijk J. Chem. Soc. Chem. Commun. 1983 1366. 63 W. E. Marsh D. S. Eggleston W. E. Hatfield and D. J. Hodgson Inorg. Chim. Acta 1983 70 137. 64 W. E. Marsh K. C. Patel W. E. Hatfield and D. J. Hodgson fnorg. Chem. 1983 22 51 1. 65 R. D. Willett and G. L. Breneman Inorg. Chem. 1983 22 326. 66 M. Mtgnamisi-Belombt and H. Endres Acta Crysrallogr. 1983 C39 707. 67 C. L. Klein E. D. Stevens C. J. O'Connor R. J. Majeste and L. M. Trefonas fnorg. Chim. Acta 1983 70 151. Cu Ag Au; Zn Cd Hg 279 A trigonal-bipyramidal Cu"[5,8,5] complex containing a tweezer-type ligand cation and a [cu2c16]2- anion has been reported.68 Studies on the tri-n-actylam- monium chloro complexes of Cu" in benzene solution have been de~cribed.~~ E.s.r.studies have been reported on complexes containing CUCI,~- and CuBr,'- (2-Amino- 1,3-thiazoline),CuCI4 73 and the promaziniumyl free radical cation tetra- chlorocuprate salt.74 contain distorted CUC~,~- ions. An anhydrous theophyllineCu" compound [Cu(C7HsN,O2),CI2] also contains a Cu" ion in a flattened tetrahedral ge~metry.,~ [Et2NH2]2(Cu3Br8)CuBr2.EtOHcontains planar symmetrically dibridged Cu3Brs2- trimers (I) and a neutral CuBr chain.76 Br The magnetic behaviour of a series of tetranuclear copper(I1) halide complexes have been explained in terms of the isotropic Heisenberg The crystal structure of the antiferromagnetic copper(r1) bromide adduct of the tetranuclear cluster (MeC5H4),Cr4( p3-0)(p3-S)3has been described.78 The pseudo-polymeric chain structure of dibromo(cyc1ohexane- 1,2-dione dioxime)copper(I I) has been Eight Cu" C1 and Br complexes with 3-aminopropan- 1-01 and its methyl derivatives have been characterized.80 The structures of two complexes of CuC12 and 1,4-oxathiane have been studied.In one complex (CuCl,) chains are cross- linked by (S-.O)bridging ligands generating both five- and six-co-ordinate Cu sites in the other the CuCI units are joined into layers by the (S...O)bridges and six-co-ordinate environments are generated.8' U.v.-visible and i.r.investigations of tetrahydrofuran-Cu" chloride solutions have been reported.82 The structure of the red Cu"-doped methylammonium tetrachloromanganate(I1) complex contains distorted octahedral The framework of a-NaCuPO is built with isolated PO tetrahedra NaO polyhedra and CuO pyramids.84 In 68 G. R. Newkome V. K. Gupta and F. R. Fronczek Inorg. Chem. 1983 22 171. 69 C. Fischer H. Wagner and V. V. Bagreev Polyhedron 1982 2 1141. 70 A. Bencini and D. Gatteschi J. Am. Chem. SOC. 1983 105 5535. 7' A. C. Massabni 0. R. Nascimento R. H. A. Santos R. H. P. Francisco and J. R. Lechat Znorg. Chim. Acta 1983 72 127. 72 R. D. Willet R. J. Wong and M. Numata Inorg. Chem. 1983 22 3189. 73 T. Glowiak M. Kubiak T. Tatarowski H. Kozlowski and M. Gosilvez Inorg.Chim. Acla 1983,80,67. 74 R. B. Von Dreele and J. Harris Acta Crystaallogr. 1983 C39 170. 75 M. B. Cingi A. M. M. Lanfredi and A. Tiripicchio Acra Crystallogr. 1983 C39 1523. 76 R. Fletcher J. J. Hansen J. Livermore and R. D. Willett Inorg. Chem. 1983 22 330. 77 D. H. Jones J. R.Sams and R. C. Thompson Inorg. Chem. 1983 22 1399. 78 A. A. Pasynokii 1. L. Eremenko Yu. V. Rakitin V. M. Novotortsev 0. G. Ellert V. T. Kalinnikov V. E. Shklover Yu. T. Struchkov S. V. Lindeman T. Kh. Kurbanov and G. Sh. Gasanov J. Organomet. Chern. 1983 248 309. 79 M. Megnamisi-Bt5lombC and H. Endres Acra Crystallogr. 1983 C39 1190. 80 T. Lindgren R. Sillanpaa T. Nortia and K. Pihlaja Inorg. Chim. Acfa 1983 73 153. 81 J. C. Barnes J. D. Paton and A.McKissock Acra Crystallogr. 1983 C39 547. 82 C. Amuli J. Meullemeestre M.-J. Schwing and F. Vierling Inorg. Chem. 1983 22 3567. 83 G. Chapuis G. Brunisholz C. Javet and R. Roulet Inorg. Chem. 1983 22 455. 84 P. M. Quarton and A. W. Kolsi Acta Crvsfollogr.,1983 C39 664. 280 J. Silver Na6[Cu2{B16024(0H)10}]. 12H20 each borate anion is ring-like and encloses two Cu" ions forming a chelate-like ~ornplex.'~ Pb2C~5(Se03)6(U02)2(oH)6.2H20 contains layers of [Cu(O OH H20),] octahedra,86 whereas in CU,(U~~)(S~O~),(~H), [Cu(O OH),] layers are found." Several studies on the preparation and structures of dimeric Cu" carboxylate adducts have appeared.*' C~CU(C~H~O~)~.~H~O contains infinite chains of alternate metal ions linked via H20 rnolecule~.~~ In (2,4,6-trimethylpyridine)2Cu(MeC02)* the co-ordination of Cu is 4 + 2.90 The structure and magnetic properties of CU,L(M~CO~)~~M~OH= anion of N,Nf-bis(2-[(o-hydroxybenzhydry-(L2-lidene)amino]-ethyl}-I ,2-ethanediamine) have been Tunable exchange interactions in poxalatocopper(i1) dinuclear complexes illustrate the possibilities of this field.92 EXAFS structure and magnetic properties of a Cu"Ni" poxalato mixed linear-chain have been reported,93 as have the structures of [Cu2(Me4en),(C2o4)(H20)21(PF,)2.2H20 and [Cu2(Et5dien)2(C204>1(pF6)2*94 Formation constants are determined for the complexes in the Cu"-nitrilotriacetate (NTA3-) parent and in the Cu"-NTA3-glycinate Cu"-NTA3-amrnonia and Cu"- NTA3-methylamine mixed-ligand equilibrium systems.95 The Cu" complex of dihydro-1 H,3 H,5H-oxazolo-[3,4-c]-oxazole-7a-carboxylic acid has been character- i~ed,~~ as have three isonicotinato N-oxide complexes.97 The formation of the esters of N-( 1,3-dioxa-5-azacyclohexyl)aceticacid via the demetallation reaction of the Cu" complex of the acid has been f~llowed,~' as have the kinetics of the Cu"-catalysed oxidation of lactic acid with chloramine T.99 The binding of amino acids to hexahydrated Cu2+ions a process presumed to occur when they are adsorbed in the interlamellar space of homoionic smectite clays has been characterized by a semiempirical m.0.method.Io0 The structure of the Cu" complex with a-aminoisobutyric acid consists of alkoxo-bridged dinuclear units."' A study of Cu" propionate adducts with diphenylphosphinoacetylene and bis(dipheny1phosphino)acetylene has been reported.lo* The structure of bis(N-tosylglycinato)bis( N-methylimidazole)Cu" shows Cu" interactions with carboxylic 115 H.Behm Acta Crysrallogr. 1983 C39 20. 86 D. Ginderow and F. Cesbron Acta Crysrallogr. 1983 C39 824. 87 D. Ginderow and F. Cesbron Actn Crvstallogr. 1983 C39 1605. nn (a) V. M. Rao D. N. Sathyanarayana and H. Manohar J. Chem. SOC.,Dalton Trans. 1983 2167; (b) M. Melnik and J. Mrozinski Z. Anorg. Allg. Chem. 1983 500 210; (c) L. C. Porter M. H. Dickman and R.J. Doedens Inorg. Chem. 1983 22 1964. 89 E. A. Klop A. J. M. Duisenberg and A. L. Spek Acta Crysrallogr. 1983 C39 1342. 90 A. Busnot F. Busnot A. Leclaire and M.Bernard Z. Anorg. Allg. Chem. 1983 503 207. 91 B. Chiari W. E. Hatfield 0. Piovesana T. Tarantelli L. W. Haar and P.F. Zanazzi Inorg. Chem. 1983 22 1468. 92 M. Julve M. Verdaguer 0. Kahn A. Gleizes and M. Philocke-Levisalles Znorg. Chem. 1983 22 368. 93 M. Verdaguer M. Julve A. Michalowicz and 0. Kahn Inorg. Chem. 1983 22 2624. 94 J. Sletten Acta Chem. Scand. 1983 A37 569. 95 F. Debreczeni and 1. Nagypal Inorg. Chim. Acta 1983 72 61. 96 S.-B. Teo and M. J. O'Connor Inorg. Chim. Acta 1983 70 107. 97 (a) H. Knuuttila and P. Knuuttila Acta Chem. Scand. Ser. A 1983 37 227; (b) H. Knuuttila Inorg. Chim. &fa 1983 72 1 I. 98 S.-B. Teo and S.-G. Teoh Inorg. Chim. Acfa 1983 68 107. 99 S. Jha P. D. Sharma and Y. K. Gupta Inorg.Chem. 1983 22 1393. I00 A. Gupta G. H. Loew and J. Lawless Inorg. Chem. 1983 22 I1 1. 101 M. M. Kuriya T. Harada H. Okawa and S. Kida Inorg. Chitn. Acta 1983 75 1. I02 M. Melnik. M. Sundberg and R. Uggla Acta Chem. Scand. Ser. A 1983 37 659. Cu,Ag Au; Zn,Cd Hg 281 oxygens at 1.967 and 2.758 A.103Complexes of diaza-crown-N,N'-dialkanoic acids with Cu" and dicopper(r1) have been obtained.lo4 Lead tetra-acetate oxidation of metallic copper to Cu2+ leads to the formation of {CU(O~CM~)~L}~ (where L = pyridine or 2- 3- or 4-methylpyridine).'05 Tetrakis( p-crotonato)bis(quinoline)dicop-per(1i) has a Cu-Cu distance of 2.66(3) &Io6 The He' photoelectron spectrum of bis(acetylacetonato)copper(II) has been measured and its electronic spectrum inter- preted by the Angular Orbital Method and Crystal Field Theory.Io7 Cu(acac) reacts with C2N2 in dichloroethane to give bis[ 1-cyano-2-( 1-iminoethy1)butane- 1,3-dionato]C~",'~~ which contains square planar Cu".Studies on Cu" triflate compounds containing aminopropanol isomers have revealed a number of hydrogen- bridged dimeric and trimeric specie^.'^' The kinetics of the reactions of P-diketones with Cu have been studied."' There is no evidence for ferromagnetic dimers in CU(C~H~NO)~(NO~)~.~" The effect of molecular cage size on the motion and co- ordination of Cu" in cross-linked poly(viny1 alcohol) gels has been studied by e.s.r."' In a series of di-p-hydroxo-bridged Cu" complexes e.s.r. spectra have been used to correlate aminotropic exchange and structure.'13 The CU" complexes of some macrocyclic crown ethers have been studied1I4 and in one complex the Cu'l ion has pentagonal-bipyramidal geometry with two CI- atoms axially co-ordinated.Solvent extraction of Cu" by high molecular weight hydroxyoximes' l5 and Cu2+ uptake by montmorillonite' I6 have been studied. Electron-spin echo spectrometry has been used to locate Cu" in X-zeoiites.II7 X-Ray studies on an aqueous solution of CuSO have established that each Cu2+ ion has a distorted octahedral arrangement of H20 molecules.' I' Electrolytic dissol- ution of Cu with dimethyl sulphoxide in SO2 was shown to give pure copper disulphate.' I9 The structures of the thiometallates [CU,MSCI](PP~~)~S [CU~MS~CI](PP~~)~O (M = W or Mo) and (PPh)3Cu2WS4.0.8CH2C12 have been reported.12' In (Ph3P)2C~( the two Cu atoms and four P atoms are virtually p-sPh),c~(PPh,)~ I03 L.P. Battaglia A. B. Corradi G. Marcotrigiano L. Manabue and G. C. Pellacani Inorg. Chem. 1983 22 1902. 104 R. A. Kolinski and J. Mrozinski Polvhedron 1983 2 1217. IU5 A. Debroy M. P. Mahajan M. N. Bhattacherjee and M. K. Chandhuri J. Chem. SOC. Dalron Trans. 1983 2531. I06 M. Bukaska-Strzyzewska J. Skoweranda E. Heyduk and J. Mrozihski Inorg. Chim.Acfa 1983,73,207. I07 (a) S. Kitagawa I. Morishima and Y. Yoshikawa Polyhedron 1983 2 43; (b) G. St. Nikolov and M. A. Atanosov Inorg. Chim. Acta 1983 12 95. I08 B. Corain M. Basato G. Visentin and G. Zanotti J. Chem. Soc. Dalton Trans. 1983 1217.109 (a)G. Nieuwpoort and J. Reedijk Inorg. Chirn. Acta 1983,71,125;(b)G. Nieuwpoort G. C. Verschoor and J. Reedijk J. Chem. Soc. Dalton Trans. 1983 531. I10 M. J. Hynes and M. T. O'Shea J. Chem. Soc. Dalton Trans. 1983 331. Ill R. L. Carlin R. Burriel R. M. Cornelisse and A. J. van Duyneveldt Inorg. Chem. 1983 22 831. I I2 D. Suryanarayana P. A. Narayana and L. Kevan Inorg. Chem. 1983 22 474. I I3 L. Banci A. Bencini and D. Gatteschi J. Am. Chem. Soc. 1983 105 761. 114 (a) A. GUI and 0. BekProjjlu J. Chem. Soc. Dalton Trans. 1983 2537; (b) A. Horbaczewski and J. F. Biernat Inorg. Chirn. Acta 1983 74 131 ;(c) T. Sakurai K. Kobayashi S. Tsuboyama Y. Kohno N. Azumo and K. Ishizu Acta Crystallogr. 1983 C39 206. llS L. Calligaro A. Mantovani U.Belluco and M.Acampora Polyhedron 1983 2 1189. I I6 P. Monsef-Mirzai and W. R. McWhinnie Inorg. Chirn.Acta 1983 73 41. I I7 T.Ichikawa and L. Kevan J. Am. Chem. Soc. 1983 105 402. 1 I8 A. Musinu G. Paschina G. Piccaluga and M. Magini Inorg. Chem. 1983 22 1184. 1 I9 N. K. Graham J. B. Gill and D. C. Goodall J. Chem. Soc. Dalton Trans. 1983 1363. I20 A. Muller H. Bogge and U. Schimanski Inorg. Chim. Acta 1983 69 5. 282 J. Silver coplanar.121 The Cu" complex of 1,4,7-trithiacyclononanecontains a nearly regular octahedral copper co-ordination. 122 Cu" complexes with 12-1 6-membered cyclic tetrathiaethers have been reported. 123 A Cu" complex of the thiosemicarbazone of a-hydroxy-P-naphthaldehydehas been isolated'24 and a stable bis(thiolate) of Cu" with long axial Cu-S linkages (2.94A) described.'25 A tetrahedrally distorted Cu" environment has been observed in a disulphide-coupled N-(2-ethanethiol)salicy-lideneimine complex.126 The structures and electrochemistry of some Cu"-mercap- tide complexes have been in~estigated.'~' The kinetics of the metal-exchange reaction of bis(8-mercaptoquinolato)nickel(11)chelate with Cu" ion have been studied by an exchange-extraction method.'28 The dinuclear Cu" complexes with 24"-(alkylthio)ethylthio]ethanol and 2-[2-(2-pyridyl)ethyIthio]ethanol both contain alko~o-bridges.'~~ [Cu3S1J3- a sulphur-rich complex has a central Cu3S3 and ring made up from three outer cus6 rings.'30 In [Cu(NH3)JBF4I2 X-ray absorption fine structure studies have provided evidence for five equal bond lengths.13' In trans-dinitratobis(0xamide oxime)cop-per(rr) the Cu has an elongated square bipyrimidal ~o-ordination.'~~ The possibility of an electronic criterion of stereochemistry of bis(chelate)copper( 11) complexes has been disc~ssed.'~~ Anation of [Cu(Me,tren)dmf12+ by NCS- N3- and Br- is charac- terized by kinetic data consistent with the operation of a dissociative interchange mechanism.134 N.m.r.relaxation studies in solutions of Cu" amines have been reported.135 Complex formation constants between 2-amino-2-(hydroxymethyl) 1pro-pane- 1,3-diol or 1 1,l -tris( N-methylaminomethy1)ethane with Ni" Cu'' Zn" and hydrogen ions have been ca1c~lated.l~~ The complexes Cu( NH3),(C5HN306).H20 and give the first evidence that an orotic acid derivative can co-ordinate Cu2+ simultaneously through the two N sites of the completely deprotonated 1igar1d.l~' A number of crystal structures of Cu" complexes containing biby (biby = 2,2'-bipyridine) have been described.They include complexes with dimeric rn~lecules,'~~ with six co-ordin- with five co-ordinated CuN2N2C chrom~phores'~~ 121 I. G. Dance P. J. Guerney A. D. Rae and M. L. Scudder Inorg. Chem. 1983 22 2883. 122 W. N. Setzer G. A. Ogle G. S. Wilson and R.S. Glass Inorg. Chem. 1983 22 266. I23 V. B. Pett L. L. Diaddario jun. E. R. Dockal P. W. Corfield C. Ceccarelli M. D. Glick L. A. Ochrymowycz and D. B. Rorabacher Inorg. Chem. 1983 22 3661. '24 Y. K. Bhoon Polyhedron 1983 2 365. 125 A.W. Addison and E. Sinn Inorg. Chem. 1983 22 1225. I26 D. M. Roundhill Polyhedron 1983 2 959. 127 G. P. Anderson C. M. Perkins and K. K. Brito Inorg. Chem. 1983 22 1267. 12* K. Haraguchi and H. Freiser Inorg. Chem. 1983 22 653. I29 (a) M. Mikuriya M. Nakam_ura H. Okawa and S. Kida Znorg. Chim. Acta 1983 68 111; (b) M. Mikuriya M. Nakamura H. Okawa and S. Kida Inorg. Chim. Acta 1983 70 223. 130 A. Muller and U. Schimanski Inorg. Chim. Acta 1983 77 L187. 131 L. Alagna. T. Prosperi A. A. G. Tomlinson and G. Vlaic J. Chem. SOC.,Dalton Trans. 1983 645. I32 (a) H. Endres N. Genc and D. Nothe Acta Crystallogr. 1983 C39 701 ;(b) H. Endres and N. Genc Acta Crystallogr. 1983 C39 704. I33 A. O'Leary S. Tyagi and B. J. Hathaway Inorg. Chim. Acta 1983 76 L89.134 S. F. Lincoln J. H. Coates B. G. Doddridge A. M. Hounslow and D. L. Pisaniello Inorg. Chem. 1983 22 2869. 135 F. Debreczeni J. PolgPr and I. Nagypd Inorg. Chim. Acta 1983 71 195. I36 (a) L. Bologni A. Sabatini and A. Vacca Inorg. Chirn.Acta 1983,69,71; (b) L. Bologni M. Micheloni A. Sabatini and A. Vacca Inorg. Chim. Acta 1983 70 117. 13' P. Arnzabalaga P. Castan and F. Dahan Inorg. Chem. 1983 22 2245. I38 B. N. Figgis R. Mason A. R.P. Smith J. N. Varghese and G. A. Williams J. Chem. Soc. Dalton Trans. 1983 703. I39 S. Tyagi and B. J. Hathaway J. Chem. Soc. Dalton Trans. 1983 199. Cu Ag Au; Zn,Cd Hg 283 ated CuN402 and CuN4X2 chrom~phores,'~~'~~ and with five co-ordinated square pyramidal Cu.'43 The spin density distributions of one of the complexes has been determined from two-dimensional polarized neutron diffraction data.13* The magnetic and spectro- scopic behaviour of a series of amine adducts of Cu"- N-acetyl-P-alaninate general formula Cu(ac-P-ala),B,. n H20(B = ethylenediamine 4-methylpyridine pyridine biby or 3-methylpyridine) has been reported.Iu Thermodynamic and spectroscopic properties of mixed-ligand complexes of Cu" with py biby 2,2' :6',2"-terpyridyl (terpy) in aqueous solution have been studied. Oxydiacetato(terpy)copper(II) dihy-drate has a distorted octahedral stereochemistry while that in [Cu(terpy)Cl,].H,O is pentaco-~rdinated.'~' The compound catena-[ p-aqua-bis(benzimidazo1e)difor-matocopper(II)] is established as a one-dimensional The binding sites stoicheiometry and thermodynamics of complex formation in aqueous solution of Cu" with 9-substituted purines have been in~estigated.'~' CUN units are found in tetrakis( 1,4,5-trimethylimidazole)copper(11)diperchlorate.14' Cu" is six-co-ordinate in CU(~~),(NCS)~ the pyridine rings can be found in two possible positions.*49 The co-ordination structures of species in the Cu"-methyl- and dimethylhistidine (1 :2) systems in aqueous solutions have been deduced from the pH-dependence of the c.d.spectra comparing the results with those for histi ti dine.'" The structure of Cu(dmpt),( NCS)2 (dmpt = a substituted pyrimidine) contains centrosymmetric dimers with two Cu atoms bridged by two NCS groups.15' Cu" structures containing 1,lO-phenanthroline or substituted varients have been described and rationalized in terms of a pseudo Jahn-Teller f~rmalism."~Rate constants for the one-electron oxidations of some Ru"' and Ru" complexes by the (dmphen),Cu" ion have been e~tablished.~~ [IrCl(PPh,),( p-dppn)( p-No)CUc1][PF& contains a nitrosyl bridging both metals.'53 An S-bonded adduct of cysteine with the [tris(2-pyridyl-methyl)amine]Cu" ion has been prepared.' 54 Cu" complexes of imidazoline ben- zimidazole benzothiazole benzotriazole and related ligands have been prepared'55 I40 C.Simmons A. Clearfield W. Fitzgerald S. Tyagi and B. Hathaway J. Chem. SOC.,Chem. Commun. 1983 189. 141 A. Sedov J. KoiiSek M. KabeSovi M. Dunaj J. J. Gaio and J. Garaj Inorg. Chim. Acta 1983 75 73.142 J. Foley D. Keenefick D. Phelan S. Tyagi and B. Hathaway J. Chem. SOC.,Dalton Trans. 1983 2333. I43 L. Antotini G. Marcotrigiano L. Menabue and G. C. Pellacani Inorg. Chem. 1983 22 141. I44 L. Menabue P. Prampolini M. Saladini and P. Morini Inorg. Chim. Acta 1983 68 157. I45 (a) G. Arena R. P. Bonomo S. Musumeci R. Purrello L. Rizzarelli and S. Sammartano J. Chem. SOC. Dalton Trans. 1983 1279; (6) N. B. Pahor G. Nardin R. P. Bonoma and E. Rizzarelli J. Chem. SOC. Dalton Trans. 1983 1797 (c)T. Rojo T. Vlasse and D. Beltran-Porter Acta Crystallogr. 1983 C39 194. I46 M. Bukowska-Strzyiewska and A. Tosik Acta Crystallogr. 1983 C39 203. I47 (a)S. Arpalahti and H. Lonnberg Inorg. Chim. Acta 1983 78 63; (b)ibid. 1983 80 25. I48 E.Bernarducci P. K. Bharadwaj K. Krogh-Jespersen J. A. Potenza and H. J. Schugar J. Am. Chem. SOC.,1983 105 3860. I49 J. Soidanovi M. KabeSovi and J. Gaio Inorg. Chim. Acta 1983 76 L203. I50 L. Casella and M. Gullotti Inorg. Chem. 1983 22 242. 151 M. B. Cingi A. M. M. Lanfredi A. Tiripicchio J. G. Haasnoot and J. Reedijk Inorg. Chim. Acta 1983 72 81. I52 (a)C. J. Simmons K. Seff F. Clifford and B. J. Hathaway Acta Crystallogr. 1983 C39 1360; (6) S. Tyagi and B. J. Hathaway J. Chem. SOC.,Dalton Trans. 1983 2693; (c) C. Escobar and 0.Wittke Acta Crvstallogr. 1983 C39 1643. I53 (a) P.Dapporto G. De Munno G. Bruno and M. Romeo Acfa Crysfallogr. 1983 C39 718; (6) G. De Munno G. Denti and P. Dapporto Inorg. Chim. Acta 1983 74 199; (c) A.Tiripicchio A. M. M. Lanfredi M. Ghedini and F. Neve J. Chem. Soc. Chem. Commun. 1983 97. I54 H. K. Beak and R. A. Holwerda Inorg. Chem. 1983 22 3452. I55 (a)J. Reedijk A. R. Sieddle R. A. Velapoldi and J. A. M. Van Hest Inorg. Chim. Acta 1983 74 109; (b) G. C. Wellon D. V. Bautista L. K. Thompson and F. W. Hartstock Inorg. Chim. Acta 1983,75271. 16'diamine}. 284 J. Silver and the unusual trimeric Cu" species [C~,(OH)(pz)~(Hpz)~(N03)~].H2O(Hpz = pyrazole) shown to consist of Cu,(OH)(pz) units with an almost flat Cu,N ring.'56 Cu" ions promote the formation of the Schiff bases between 2-formylpyridine and amino acids in neutral aqueous Bis-p-[ N,N'-ethylenebis(pyrrol-2-ylmethyleneaminato)]dicopper(~r) is a dimer where each of the intertwined Schiff bases binds two Cu atoms.'58 Condensation of &&triketone with aliphatic amines and Cur' complexes of the Schiff bases has been studied the products are mono- n~c1ear.l~~ Cyclic voltammetry of four dinuclear Cu" I ,3,5-triketonates and their diamine Schiff-base derivatives has been investigated in DMF with Et,NClO as the supporting electrolyte.'60 Cu" complexes of 5-nonylsalicylaldoxime with pyridine and ammonia form five-co-ordinate adducts.16' A number of studies on (salicylal- diminato)copper(I I) salts have been reported.162 Kinetics of hydrolysis of N-salicy-lidene-2-aminopyridine have been investigated in aqueous 5% MeOH in the presence and absence of CU".'~~ Aqua-bis(N-salicylidene-P-alaninate)dicopper(I I) monohy-drate contains two differently co-ordinated Cu atoms in a dimeric molecule.'64 A spectroscopic study was reported of 1 :1 Cu" complexes of Schiff base ligands derived from ~alicylaldehyde.'~~ The reaction of P-keto-enolate and Schiff -base complexes of Cu" with cyanogen in chlorinated solvents gives cyanoimino- substituted organometallic rings.'66 A dinuclear complex of Cu" is generated by reaction of bis(salicylaldehyde)copper(Ir) with rn-xylylenebis(2-(propane-1,3-A new type of .rr-molecular complex containing dinuclear triketone Cu" complexes and benzene has been reported.168 A tetrameric Cu" complex with a Schiff base derived from pyridoxal and 2-amino- I -(3',4'-dichlorophenyl)ethanol contains a CU404 core.169 The kinetics of ligand substitution in bis( N-alkylsalicy- lideneiminato)copper(II) complexes have been studied in solvent mixtures.I7O A number of Cu" complexes of Schiff bases derived from 1-(pyrrol-2-y1)butane-1,3-dione heptane-2,4,6-trione 1 -(0-hydroxypheny1)butane- 1,3-dione and 1,2-diaminoethane have been prepared and studied by X-ray crystal structure analysis. 171 E.s.r. studies on the ligation of dimeric and tetramic Cu" complexes with Schiff I56 F. 9. Hulsbergen R. W. M. ten Hoedt G. C. Verschoor J. Reedijk and A. L. Spek J. Chem. SOC. Dalton Trans. 1983 539. I57 L. Casella and M.Gullotti Inorg. Chem. 1983 22 2259. T. Kikuchi C. Kabuto H. Yokoi M. Iwaizumi and W. Mori J. Chem. SOC.,Cbern. Commun. 1983 1306. I59 V. Drevenkar A. Deljac Z. Stefanac and J. Seibl. Polyhedron 1983 2 447. 160 R.L. Lintvedt and L. S. Kramer Inorg. Chem. 1983 22 796. 161 9. McCudden P. O'Brien and K. R.Thornback J. Cbem. SOC.,Dulton Trans. 1983 2043. I62 (a) N. S. Biradar G. V. Karajagi T. M. Aminabhavi and W. E. Rudzinski Inorg. Chim. Acta 1983 77 L107 (b) W. Steurer and W. Adlart Acta Crystallogr. 1983 B39 721 (c) ibid. B39 718; (d) F. C. Priolo E. Rotondo G. Rizzardi G. Bruno and G. Bombieri Acta Crystallogr. 1983 C39 550. 163 A. C. Dash 9. Dash P. K. Mahapatra and M. Patra J. Chem. SOC.,Dalton Trans. 1983 1503. '6.1 P.-E. Werner A. Valent V. Adelskold and 0. Svajlenova Acta Chem. Scand. Ser. A 1983 37 51. M. P. Wagner and A. Walker Znorg. Chern. 1983 22 3021. I66 9. Corain M. Basato A. Del Zotto and G. Zanotti Inorg. Chem. 1983 22 2744. 167 B.C. Whitmore and R. Eiserberg Inorg. Chem. 1983 22 1. I68 J. F. Wishart C. Ceccarelli R. L. Lindvedt J. M. Berg D. P. Foley T. Frey J. E. Hahn K. 0.Hodgson and R. Weis Inorg. Chem. 1983 22 1667. 169 L. Watz H. Paulus W. Hasse H. Langhof and F. Nepveu J. Cbem. SOC.,Dalton Trans. 1983 657. I7O H. Elias H. Miith M. Sahm H. Volz and K. J. Wannowius Inorg. Chim.Acta 1983 68 163. 171 (a) H. Adam N. A. Bailey D. E. Fenton and M. S. L. Gonzalez J. Chem. SOC.,Dalton Trans. 1983 1345; (b)J.-P. Costes and D. E. Fenton J. Chem. SOC.,Dalton Trans. 1983 2235; (c) N. A. Bailey K. C. Cox C. P. Falshaw D. E. Fenton S. E. Grundy P. Haigh C. A. Philips and T. J. King J. Chem. SOC.,Dalton Trans. 1983 2241. Cu,Ag Au; Zn Cd Hg 285 bases in solution have established the presence of both distorted tetrahedron and square pyrimidal co-~rdinations.'~~ Asymmetric synthesis of threonine and partial resolution and retro-racemization of a-amino acids via Cu" complexes of their Schiff bases has been reported.173 MucrocycZic Systems containing Copper(11). E.s.r. spectra of a series of spin-labelled Cu" tetraphenyl porphyrins have enabled electron-electron coupling constants to be ~btained."~ Comparisons of the electronic structure of BsS16 the porphine dianion and their Cu" complexes using extended Hiickel calculations have been made.'75 Studies on metal-protoporphyrin IX iron(II1) complexes are compared with those of Cu"-protoporphyrin IX iron(II1) in which the Cu" is co-ordinated to the propionate groups.76 Electronic environments of Cu" chelates of tetra-2,3- pyridinoporphyrazine and phthalocyanines are found to be similar from e.s.r. data.'77 Cu" phthalocyanines have been incorporated in apomyogl~bin.'~~ The structure of [Cu(cyclarn)(SC,F,),] (SC6FS = pentafluorothiophenolate) is tetragonally elongated in a square arrangement.'79 Dissociation kinetics of (ruc-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetra-azacyclotetradecane)copper(II) cation in strongly acidic media have shown that at least two factors contribute to the observed rates of the cleavages of the first and second M-N bonds.'" The Cu redox chemistry of a number of Cu" poly-aza macrocylces of varying size and denticity has been studied."' The stabilities of Cu poly-azacrown ether and nitrogen-oxygen macrocyles have been considered."* Seven mixed-valence dinuciear Cuii-Cu' complexes of macrocyclic ligands were used to study factors affecting intramolecular electron transfer.'83 A number of studies on dinuclear Cu" macrocycles have appeared detailing structure and electro- chemical properties. 84 The tridentate macrocyclic ligand tribenzo[b,f;j] [1,5,9]triazacyclododecine forms a bis complex with Cu" that exhibits a dynamic Jahn-Teller di~tortion."~ The distances of the protons of guest molecules to a I72 J. Jezierska A. Jezierska B. Jezowska-Tizebiatowska and A. Ozarowski Inorg. Chim. Acta 1983 68 7. I73 Yu. N. Belokon I. E. Zel'tzer V. I. Bakhmutov M. B. Saporovskaya M. G. Ryzhov A. I. Yanovsky Yu. T. Struchkor and V. M. Belikov J.Am. Chem. SOC.,1983 105 2010. I74 (a) K. M. More G. R. Eaton and S. S. Eaton Inorg. Chem. 1983 22 934; (b) R. Damoder K. M. More G. R. Eaton and S. S. Eaton J. Am. Chem. SOC.,1983 105 2147. 175 B. M. Gimarc and J.-K. Zhu Inorg. Chem. 1983 22 479. 176 B. Lukas J. Silver I. E. G. Morrison and P. W. C. Barnard Inorg. Chim. Acta 1983 78,205. 177 T. D. Smith J. Livorness H. Taylor J. R. Pilbrow and G. R. Sinclair J. Chem. SOC.,Dalton Trans. 1983 1391. 178 L. Trynda Inorg. Chim. Acta 1983 78,229. 179 A. W. Addison and E. Sinn Inorg. Chem. 1983 22 1225. B.-F. Liang and C. S. Chung Znorg. Chem. 1983 22 1017. 181 (a) M. J. Maroney and M. Wicholas Inorg. Chim. Acta 1983 77,L237; (6) L. Fabbrizi A. Poggi and P. Zanello J. Chem. SOC.Dalton Trans.1983 2191; (c) L. Fabbrizi A. Perotti and A. Poggi Inorg. Chem. 1983 22 141 1. I82 (a) V. J. Thom and R. D. Hancock Inorg. Chim. Acta 1983 77,L231; (b) E.Luboch A. Cygani and J. F. Biernot Inorg. Chim. Acta 1983 68 201. R. C. Long and D. N. Hendrickson J. Am. Chem. SOC.,1983 105 1513. I83 I84 (a) V. McKee and J. Smith J. Chem. SOC.,Chem. Commun. 1983 1465; (b)M. Yamashita H. Ito and T. Ito Inorg. Chem. 1983 22 2101; (c) K. D. Karlin J. C. Hayes J. P. Hutchinson and J. Zubieta J. Chem. SOC.,Chem. Comrnun. 1983 376; (d) S. K. Mandal and K. Nag J. Chem. Soc. Dalton Trans. 1983 2429; (e) S. M. Nelson F. Esho A. Lavery and M. G. B. Drew 1.Am. Chem. SOC. 1983 105 5693; (f)S. M. Nelson and C. V. Knox J.Chem. Soc. Dalfon Trans. 1983 2525; (g) C. Y. Ng A. E. Martell and R. J. Motekaites Inorg. Chem. 1983 22 721. 185 R. I. Sheldon A. J. Jircitano M. A. Bero J. M. Williams and K. B. Mertes J. Am. Chem. SOC.,1983 lM 3028. 286 J. Silver paramagnetic Cu" macrobicyclic complex were estimated from ' H n.m.r. relaxation times.IS6 Copper(zi1). The stabilization of co-ordinated Cu"' by the tetra-aza macrocyclic dioxocyclam has been reported. A Cu1''-deprotonated-peptidecomplex of tri a-aminoisobutyric acid contains Cu" in a square planar geometry there is little evidence of axial co-ordination.'" Cu" diethyldithiocarbamates disproportionate into Cu"' and Cu' complexes.'88 The electrochemical production and isolation of tetrakis(pyridine N-oxide)copper(r~~) hexafluorophosphate in liquid SO2 has been inve~tigated"~ and the self-exchange rates for five Cu"'-'' peptides deterrnir~ed.'~' Mixed Vulence Complexes.Studies on the Cu20-CuO-Ta205 system have identified Cu3Ta,09 and Cu5Ta 1030.191 A series of seven dinuclear Cu"-Cu' complexes of macrocyclic ligands have been prepared,Is3 as has CU"CU'(C~H~NS)~C~~.'~~ The mixed valence cluster CU~(BTA)~(~-C~H~NC)~ [BTA = benzotriazolato( 1-)] has a compressed octahedral Cu" surrounded by four tetrahedrally co-ordinated Cu' ions.193 Simple electron-transfer reactions involving Cu"'*"( N4) couples have been examined (N4 = a tetra-aza macrocyclic ligand).'94 The complex [Cu,O(n-PrL'),]- (C104),.2H20 is isolated by electrolytic oxidation of the corresponding Cu"13 com- plex in acetonitrile and has a nearly planar triangular Cu1''Cu2"O core /"-cr N\* \ /*\ cu 1 (N CU "'& 'N Bioinorganic and Biological Copper.The tight binding of mono-olefins characteristic of the ethylene receptor site of plants has been found in some Cu' complexes.30 Tetranuclear Cu' thiolate complexes (3) have been examined in relation to the metal binding site of yeast copper thi0nei11.I~~ [Cu(dmphen),]+ forms complexes with some biologically relevant sulphur amino acids.I9' I86 W.-L. Kwik N. Herron K. Takeuchi and D. Busch J. Chem. SOC.,Dalton Trans. 1983 409. I87 L. L. Diaddario W. R. Robinson and D. W. Margerum Inorg. Chem. 1983 22 1021. I88 J.-P. Barbier R. P. Hugel and C. Kappenstien Inorg. Chim.Acta 1983 77 L117. I89 P. R. Sharp and A. J. Bard Inorg. Chem. 1983 22 3462. 190 J. M. Anast A. W. Hamburg and D. W. Margerum Inorg. Chem. 1983 22 2139. 19' P. N.W. Ilunga Acta Chem. Scand. Ser. A 1983 37 117. I92 W. E. Marsh W. E. Hatfield and D. J. Hodgson inorg. Chem. 1983 22 2899. I93 G. F. Kokoszka J. Baranowski C. Goldstein J. Orsini A. D. Mighell V. L. Hines and A. R. Siedle J. Am. Chem. SOC.,1983 105 5627. I94 K. Kumar F. P. Rotzinger and J. F. Endicott J. Am. Chem. SOC.,1983 105 7064. 195 D. Datta and A. Chakravorty Znorg. Chem. 1983 22 161I. 196 M. Linss M. G. Weller and U. Weser. Inorg. Chim. Acta 1983 80 201. 19' W.-L. Kwik K.-P. Ang and P.-C. Lau 1. Chern. SOC.,Dalton Trans. 1983 2269. Cu Ag Au; Zn Cd Hg Bis[4(n-propylmercaptomethyl)imidazole]copper(rr) diperchlorate contains Cu" co-ordinated by two thioether S atoms and two imidazole N atoms and is used as a model for blue copper ~r0teins.l~~ Cu" complexes of macrocyclic ligands are suggested as models for square-pyrimidal metal active-sites of CU" complexes of bleomycin and g1~tathione.l~~ Dicopper complexes of macrocyclics have been pro- posed as models for copper protein^."^ Diaquabis(2,6-dihydroxybenzoato)cop-per(r1) has a polymeric nature each Cu being in tetragonally distorted octahedral co-ordination;'OO it is claimed as a model for metal ions in humic acids."' Complexes of Cu" dipeptides with hexacyanoferrate(rr1) are proposed as models for the reaction of galactose oxidase with ferricyanide.20' A refined model that mimics the type I1 Cu" site in galactose oxidase has been reported.202 The Cu"-semiquinonato complex as a redox intermediate may be pertinent to the chemistry of related systems in biology.203(P-SP~)~CU~(PP~~)~ has a structure which is pertinent to the conforma- tions of metallo-cysteine proteins.204 Cu" complexing by the growth stimulating tripeptide glycylhistidyllysine has been studied in blood pla~rna.~" Research continues into vitamin B6 chemistry; quarternary complexes and the structures of two complexes of bis(N-t-butyl- pyridoxylideneiminato)copper(r I) have been described.206 The effect of Mg+ ions on Cu"-alkaline phosphatase has been investigated with respect to the Cu co- ordination in the presence and absence of inorganic phosphate at ~H6.0.~" The interaction of Cu" with human lactoferrin has been studied.208 Derivatives of the I 98 N.Aoi G. Matsubayashi and T. Tanaka J. Chem. SOC.,Dalton Trans. 1983 1059. 199 K. Miyoshi H. Tanaka E. Kimura S. Tsuboyama S. Murata H. Shimizu and K. Ishizu Inorg. Chim. Acta 1983 78 23. 200 F. Cariati L. Erre G. Micera A. Panzanelli C. Ciani and A. Siron Inorg. Chim. Acta 1983 80 57. 20 1 T. S. Srivastava and S. V. Deshpande Inorg. Chim. Acta 1983 78 37. 202 R.D. Bereman G. D. Shields J. R. Dorfman and J. Bordner J. Inorg. Biochem. 1983 19 75. 203 S. Harmalker S. E. Jones and D. T. Sawyer Inorg. Chem. 1983 22 2790. 204 I. G. Dance L. J. Fitzpatrick and M. L. Scudder J. Chem. Soc. Chem. Commun. 1983 546.205 P. M. May J. Whittaker and D. R.Williams Inorg. Chim. Acta 1983 80 L5. 206 (a) H. M. Marafie M. S. El-Ezaby and A. S. Shawali Polyhedron 1983 2 775; (b) F. Bigoli M. Lanfranchi E. Leporati and M. A. Pellinghelli Inorg. Chim. Acta 1983 80 135. 207 I. Bertini C. Luchinat A. Scozzafava A. Maldotti and 0.Traverso Inorg. Chim. Acta 1983 78 19. 208 E. W. Ainscough A. M. Brodie S. J. McLahlan and V. S. Ritchie J. Inorg. Biochem. 1983 18 103. 288 J. Silver red-violet cluster of Cu and penicillamine have been prepared209 and Cull' complexes of thyrotropin releasing factor The Cu binding centre of Cu-thioein from Saccharomyces cerevisiae has been investigated using EXAFS2" The effects of pH and redox inactive complexes on reactions of parsley plastocyanin with different inorganic redox partners have been Cytochrome-f binds at the negative patch on pla~tocyanin.~'~ In cyto- chrome oxidase the secondary structure of subunit I1 has been assigned and a Cu-binding site A 'H n.m.r.study of Cu" carbonic anhydrase in the presence of bicarbonate has been reported.215 The type-3 Cu site in metal-depleted Rhus vernicifera laccase has been Enzyme-bound Cu of dopamine p-mono-oxygenase has been studied catalytically after addition of an excess of Cu A Cu" tris-complex of a pyrimidine-derived ligand is reported to have [CuN,] in D3symmetry; the ligand may be an anti-tumour agent."' The oxygen co-ordinating uracil complexes of Cull and other MI1 ions have been Co-ordination structures in the Cu"-L-histidine (1 :2) system have been deduced220 and conforma- tion analysis and studies on hydration models of Cu threoninates and isoleucinate carried out.22' The hydrogen bonding in the Cu"-saccharin complex is significantly different to that of the analogous Fe Co and Ni complexes.222 The Cu" complex of 2'-deoxyguanosine 5'-monophosphate (5'-dGMP) has been studied to establish a corre- lation between spectral changes and the N(7) co-ordination site perturbation on the 5'-dGMP Ternary 2,2'-bipyridine and phen with Cu" dipeptide com- plexes have square pyrimidal geometries and the possible modes of their action with cancer cells have been The thermal decomposition of L-tryp-tophanatocopper(I1) has been examined to try to obtain tryptamine more economi- ally.^^^ The spectral properties of Cu" complexes of barbiturates have been reported.226 Silver.-A useful source of reference on silver chemistry can be found in 'Silver summaries' from the current world literature.227 20Y M.E. Cooke M. E. McDaniel S. R. Janes S. L. Jones N. Trobak B. C. Craytor D. R. Bushman and J. R. Wright J. Inorg. Biochem. 1983 18 313. 210 G. Formicka-Kozlewska M. Bezer and L. D. Pettit J. Inorg. Biochem. 1983 18 335. 21 I J. Bordas M. H. J. Koch H.-J. Hartmann and U. Weser Inorg. Chim. Acta 1983 78 113. 212 (a) S. K. Chapman A. D. Watson and A. G. Sykes J. Chem. SOC.,Dalton Trans. 1983,2543 (b) S. K. Chapman I. Sanemasa and A. G. Sykes ibid. 2549. 213 D. Beoka-Bets S. K. Chapman C. V. Knox and A. G. Sykes J. Chem.SOC.,Chem. Commun. 1983,1150. 214 (a) M. Lundeen J. Inorg. Biochem. 1983 18 I; (b) ibid. 1983 19 179. I. Bertini E. Canti C. Luchinat and E. Borgi J. Inorg. Biochem. 1983 18 221. B. Reinhammar J. Inorg. Biochem. 1983 18 113. T. Skotland and T. Ljones J. Inorg. Biochem. 1983 18 I I. N. Saha and D. Mukherjee Polyhedron 1983 2 47. A. R. Sarkar and P. Ghosh Inorg. Chim.Acta 1983 78 L39. L. Casella and M. Gulloti J. Inorg. Biochem. 1983 18 19. N. Raos and V. J. Simeon J. Inorg. Biochem. 1983 18 135. S. K. Haider K. M. A. Malik K. J. Ahmed H. Hess H. Riffel and M. B. Hursthouse Inorg. Chim. 215 216 217 218 219 220 22 I 222 Acta 1983 72 21. 223 Ajmir-Riahi and T. Theophanides Inorg.Chim. Acta 1983 80 223. 224 S. V. Despande and T.S. Srivastava Inorg. Chim. Acta 1983 78 75. 225 P. Gili and K. de la Fuente Inorg. Chim. Acta 1983 78 L5. 226 A. Pezeshk F. T. Greenaway and J. R. J. Sorenson Inorg. Chim.Actu 1983 80 191. 227 The Silver Institute. Suite 1138 1001 Connecticut Avenue N.W. Washington D.C. 20036. Cu Ag Au; Zn,Cd Hg 289 Silver Heterornetallic Clusters. Heterometallic adducts of [Rh6(co)15c]'- including the double- and triple-decker sandwich compounds [Ag,{Rh,(CO)i5C}2]4-" (n = I and 3) and [Ag,{Rh,(C0)iSC}3]6-" (n = 2 or 4) and the X-ray structure of [PPh4]3[Ag{Rh6(CO)l 5C}2] have been reported.228 [Ag{Rh(CO)(PPh3)( T-C~H~)}~] [PF,].C,H,Me contains a near linear Rh-Ag-Rh framework.229 The synthesis and characterization of [Ag2Pt( p-S)4(PPh3),](BF4)2.0.25CHC13has been described both Ag+ ions are linearly co-ordinated to the S atoms the small bite distance of the [R2(P-S)~(PP~~)~] ligand leads to an Ag.-.Ag contact distance of only 2.8 15 A.230 Triangular Fe- Ag clusters of the type [Fe,Ag(Co),{CHC(C,H,)( NRR')}P(C,H5)2]X have been reported.231 Silver(I). The structure of silver pyrovanadate Ag4V207 is described as the C.C.P. silver metal structure in which some Ag atoms are replaced by V207 groups and others are shifted.232 Di-silver(I) decachlorodioxotetra-aluminate(rII) Ag2[AI4CIi0O2],contains [A14C1,002]2- and Agf ions the latter are co-ordinated by five chlorines in a distorted trigonal-bipyramidal arrangement.233 Precipitation reac- tions between silver nitrate and sodium tungstate have been studied by poten- ti~metry.'~~ Ag(NH,)2N03 contains linear diamine Ag moieties at 223 K235and in CsAgCI at 170"C the Ag' has a trigonal-bipyramidal ~o-ordination.'~~ Structures of eleven melts of different compositions in the systems (Ag.K.Na)(I NO3) have been studied.237 Structures of [Ag(L)X] where L = 2 I 1-bis(diphenylphosphino)-methyl-benzo[c]phenanthrene and where X = C1 (A) SnCI (B) NO3 (C) and C104 (D) have been rep~rted.'~' The Ag atom in A shows a distorted trigonal co-ordination to two P atoms and one CI atom.238 The Ag atoms in B-D are formally four co-ordinated.Electrochemical studies of chloro-complex formation in chloroalumi- nate melts indicated that Ag' forms stable mononuclear complexes of the type AgCl,'-P(2 d p d 4) in the chloride ion-rich compositions.239 The reaction of (CF3C02)Ag with LiR gives [Bu4N][AgR2](R = C6F5 or c6c1s).240 Reaction of Ag C 1O4 with 2,5 -di met h y1-2,5 -di -isocy ano he xan e (TM B) inmethano I-t oni t ril e yields [Ag2(TMB)]3(C104)3.It consists of pairs of -..AgCN NCAgCN NCAg... infinite chains containing the TMB ligand in an extended form.24i Both I 1 and 2:3 adducts of cyclo-octotatetraene and AgN03 have been reported the former 228 B. T. Heaton L. Strona S. Martinengo D. Strumolo V. G. Albano and D. Braga J. Chem. SOC.,Dalton Trans. 1983 2175. 229 N. G. Connelly R. LUCY,J. D. Payne A. M. R. Gahas and W. E. Geiger J. Chem. SOC.,Dalron Trans. 1983 1879. 230 C. E. Briant T.S. A. Hor N. D. Howells and D. M. P. Mingos J. Organomet. Chem. 1983 256 C15. 23 I G. N. Matt N. J. Taylor and A. J. Carty Organomerallics 1983 2 447. 232 R. Masse M. T. Averbuch-Pouchot A. Durif and J. C. Guitel Acta Crystallogr. 1983 c39,1608. 233 D. Jentsch P. G. Jones E. Schwarzmann and G. M. Sheldrick Acta Crystallogr. 1983 C39 1173. 234 J. B. Jensen and J. Lou Acta Chem. Scand. Ser. A 1983 37,617. 235 T. Yamaquchi and 0. Lindqvist Acta Chem. Scand. Ser. A 1983 37,685. 236 H.-C. Gaebell G. Meyer and R. Hoppe Z. Anorg. Allg. Chem. 1983 497,199. 237 B. Holmberg and G. Johansson Acfa Chem. Scand. Ser. A 1983 37,367. 238 M. Barrow H.-B. Burgi M. Camelli F. Caruso E. Fisher L. M. Venanzi and L. Zambonelli Inorg. Chem. 1983 22 2356.239 T. M. Laher and C. L. Hussey Inorg. Chem. 1983 22 1279. R. Uson A. Laguna and J. A. Abad. J. Organorner. Chem. 1983 246 341. A. Guitard A. Mari A. L. Beauchamp Y.Dartiquenave and M. Dartiquenave Inorg. Chem. 1983,22 240 24 I 1603. 290 J. Siluer Q consists of strongly bonded Ag'-C8H8 units linked by weaker Ag-ligand interac- tion~.~~~ Bis(1,2:5,6-7-cyclo-octatetraene)silver(~)nitrate exists as discrete molecules in the crystalline state (4).242' Benzocyclo-octatetraensilver(1) perchlorate is an example of a silver ion co-ordinated to an arene and an olefin ligand simultane~usly.~~~ Structures of [{Ag[C,(C02Me)s](OH)2}n]-1.5nH20,[{Ag[Cs(C0,Me)s](PPh3)}2] and [Ag{C,(C02Me),}(PPh,),1 have been reported Ag-C bonding interactions are found in the first two complexes.244 The structure of mesitylsilver(1) shows it to be tetranuclear [Ag(2,4,6,-Me3C6H2)I4 in the solid state.245 The interaction of Ag' with P-disulphone carbanions in aqueous alkaline media have been reported; a P-(5) 242 (a) W.C. Ho and T. C. W. Mak 1.Organomet. Chem. 1983 241 I31 ;(b) ibid. 1983 246 331;(c) ibid. 1983 243 233. 243 T. C. W. Mak W. C. Ho,and N. Z. Huang J. Organomet. Chem. 1983 251 413. 244 M. I. Bruce M. L. Williams B. W. Skelton and A. H. White J. Chem. SOC.,Dalton Trans. 1983 799. 245 S. Garnbarotta C.Floriana A. Chiesi-Villa. and C. Guastini J. Chem. Soc. Chern. Commun. 1983. 1087. Cu,Ag Au; Zn Cd Hg 29 1 disulphone carbanion with Ag' is an example of an sp3 carbon bonded to Ag' (5).,, Silver alkene-complexes their stoicheiometries stabilities and ' H n.m.r.bound shifts have been reported.247 Some silver(1) complexes [Ag(am),]NO (where am = phen or biby) have been studied using secondary ion mass spectrometry248 and the stability constants of Ag' complexes of N-methyl substituted 4-methyldiethylenetriamines in aqueous solution at 25 "C determined.249 [Tetrakis(tetrasulphur tetranitrogen dioxide)sil- ver((r)]+[AsFJ contains the Ag atoms 0.53 8 below a square of 4N atoms.250 catena-Bis( p-benzoato-O,O',p-O)bis(pyridine)disilver(I) contains Ag co-ordinated in a distorted tetrahedron to one N and three 0 atoms a similar environment is found in bis[ p-phthalato(tri pyridine)disilver(~)] for one Ag but the other forms almost a plane with the nearest two N and two 0 atoms.25' Single-crystal e.p.r.spectra of two spin-labelled Ag porphyrins doped in Zn tetraphenylporphyrin have been obtained.252 (PPh,),Ag2MoS,~0.8CH2C12 contains a doubly bridging MoS,~-ligand generating a nearly linear Age. eM0.a .AgP moiety with one tetrahedrally and one trigonal-planar co-ordinated Ag atom.253 [Ag,{ S(NSO),},][AsF,],.SO contains two crystallographically independent Ag atoms.254 The structure of (cyclo-L-methionylglycine)silver( I) nitrate consists of infinite linear arrays of Ag atoms doubly bridged by methionine S atoms and nitrate The intertwined double (-Ag-SR-),-strand chain-structure of crystalline (3-methylpentane-3-thio1ate)sil-ver has been described in relation to (AgSR)s molecules in solution.256 Silver(1) salts have been used as one-electron and two-electron oxidants in their reactions with [Fe2(~-C5H5)2(C0)4-n(CNMe)n] derivatives (n = O-2).257 Silver-catalysed macrocyclic ether formation has been studied.[(CH2O),Ag2][Ag][AsF,] contains a novel twelve-membered macrocyclic ether.258 The mechanism of the Ag-catalysed epoxidation of ethylene has been investigated.259 Studies of the precipitation of Ag20 within unilamellar vesicules have been reported.260 Evidence has been presented against ion-pair formation in the reaction of ethyl halides with Ag salts in ethanol2,' and the salts Z[AuR2] (Z = Ag(C4HgS) or Ag R = C6F3H2or C,F5) have been prepared.262 246 J. R. DeMember H. F. Evans F. A. Wallace and P.A. Tariverdian J. Am. Chem. SOC.,1983 105 5647. 247 W. Offerman and U. Fritzsche Inorg. Chim. Ana 1983 73 113. 248 J. L. Pierce K. L. Busch R. G. Cooks and R. A. Walton Znorg. Chem. 1983 22 2492. 249 J. Yperman J. Mullens J.-P. Francois and L. C. Van Poucke Inorg. Chem. 1983 22 1361. 250 H. W. Roesky M. Thomas H. G. Schmidt W. Clegg M. Noltemeyer and G. M. Sheldrick J. Chem. SOC.,Dalton Trans. 1983 405. 25' (a) M. Hedrich and H. Hartl Acta Crysrallogr. 1983 C39 533; (b) ibid. 1983 C39 1649. 252 R. Damoder K. M. More G. R. Eaton and S. S. Eaton Inorg. Chem. 1983 22 3728. 253 A. Muller H. Bogge and U. Schirnanski Inorg. Chim.Acta 1983 69 5. 254 H. W. Roesky M. Thomas P. G. Jones W. Pinkert and G. M.Sheldrick J. Chem. SOC. Dalton Trans.1983 1211. 255 G. Valle and R. Eltore J. Chem. SOC.,Dalton Trans. 1983 453. 256 I. G. Dance L. J. Fitzpatrick A. D. Rae and M. L. Scudder Inorg. Chem. 1983 22 3785. 257 B. Callan and A. R. Manning J. Chem. SOC.,Chem. Commun.,1983 263. 258 H. W. Roesky E. Peymann J. Schimkowiak M. Noltemeyer W. Pinkert and G. M. Sheldrick J. Chem. SOC.,Chern. Commun.,1983 981. 259 R. €3. Grant and R. M. Lampert J. Chem. SOC.,Chem. Commun.,1983 662. 260 S. Mann and R. J. P. Williams J. Chem. SOC.,Dalron Trans. 1983 31 1. 26 1 D. N. Kevill and E. K. Fujimoto J. Chem. SOC.,Chem. Commun.,1983 1149. 262 K. Moss R. V. 'D'Parish. A. Laguna M. Laguna and R. Uson J. Chem. SOC..Dalton Trans. 1983,2071. 292 J. Silver Silver( 11). Secondary ion mass spectrometry was used to study [Ag(biby)2]S208 and [Ag(~y)~]S~o~.~~* and the structure of the [2.2.2] paracyclophane (C24H24) complex of Ag" has been reported.263 Silver(1rz).Both the kinetics and mechanism of H202oxidation by Ag"' in aqueous alkaline media,264 and the kinetics of reduction of the tetrahydroxoargentate(lI1) ion by arsenite have been studied by stopped-flow ~pectrophotornetry.~~~~ Gold.-Gold Heterometallic Complexes. A number of papers dealing with gold atoms in heterometallic clusters and in gold clusters have been p~blished.~~**~~~-~~* Details of the structural information obtained on these clusters is in Table 1. The reactivity of [Aug(PPh3)J3+ and [Au8(PPh3),I2+ towards isopropyl isocyanide has been studied,279 the electrochemical reduction of the former cluster has also been de~cribed.~"~ The e.s.r.spectrum of matrix isolated Au3 has been observed.280 Gold(1).[(C,Me,)Rh( ~U-L)AUP(C~H~)~](CIO~)~.CH~C~~ (where L = N-indolyl) and [(PhP,),Au,( p-bbzim)Rh(cod)][C10,1.CHC13 (where bbzim = dianion of 2,2'-bibenzimidazole and cod = cyclo-octa- 1,5-diene) both contain Au atoms in essen- tually linear co-ordinations.'*' The preparations of heterodinuclear Rh'-Au' or Ir'-Au' indoyl-bridged complexes of the type [(diolefin)M( 77-Tn)AuPR,]+ (M = Rh; diolefin = cod tetrafluorobenzobarrelene = TFB or Me,TFB; M = Ir; 2h3 C. Cohen-Addad P. Baret P. Chautemps and J. L. Pierre Acta Crystallogr. 1983 C39 1346. 264 (a)E. T. Borish and L. J. Kirschenbaum J. Chem. Soc. Dalton Trans. 1983,749; (b)L.J. Kirschenbaum and J. D. Rush Inorg. Chem. 1983 22 3304. 265 L. J. Farrugia M. J. Freeman M. Green A. G. Orpen F. G. A. Stone and I. D. Slater J. Organomet. Chem. 1983 249 273. 266 L. W. Bateman M. Green K. A. Mead R. M. Mills I. D. Slater F. G. A. Stone and P. Woodward J. Chem. SOC.,Dalton Trans. 1983 2599. 267 M. I. Bruce and B. K. Nicholson J. Organomet. Chem. 1983 252 243. 268 B. F. G. Johnson J. Lewis J. N. Nicholls J. Puga and K. H. Whitmire J. C'hem. SOC.,Dalton Trans. 1983 787. 269 A. G. Cowie B. F. Johnson J. Lewis J. N. Nicholls P. R Raithby and M. J. Rosales J. Chem. Sac. Dalton Trans. 1983 23 11. 270 B. F. G. Johnson J. Lewis W. J. H. Nelson J. Puga P. R. Raithby D. Braga M. McPartlin and W. Clegg J. Organornet.Chem. 1983 243 C13. 27 I K. Burges B. F. G. Johnson D. A. Kaner J. Lewis P. R. Raithby S. N. Azman and B. Syad-Mustaffa J. Chem. SOC.,Chem. Commun. 1983 455. 272 K. Burges B. F. G. Johnson J. Lewis and P. R. Raithby J. Chem. SOC.,Dalton Trans. 1983 1661. 273 B. F. G. Johnson J. Lewis W. J. H. Nelson M. D. Vargas D. Braga and M. McPartlin 1.Organomet. Chem. 1983 246 C69. 274 A. L. Casalnuovo L. H. Pignolet J. W. A. van der Velden J. J. Bour and J. J. Steggerda J. Am. Chem. SOC.,1983 105 5957. 275 R. A. Awang G. A. Carriedo J. A. K. Howard K. A. Mead 1. Moore C. M. Nunn and F. G. A. Stone J. Chem. SOC.,Chem. Commun. 1983 964. 276 (a) K. Burgess B. F. G. Johnson and J. Lewis J. Organomet. Chem. 1983,247 C42; (b)J. Chem. SOC. Dalton Trans.1983 1179. 277 C. E. Briant K. P. Hall and D. M. P. Mingos J. Organomef. Chem. 1983 254 C18. 278 J. W. A. Van der Velden J. J. Bow W. P. Bosman and J. H. Noordik Inorg. Chem. 1983 1913. 279 (a) W. Bos J. J. Bour J. W. A. Van der Velden J. J. Steggerda A. L. Casalnuovo and L. H. Pignolet J. Organomet. Chem. 1983 253 C64; (b) J. G. M. van Linden M. L. H. Paulissen and J. E. J. Schmitz J. Am. Chem. SOC.,1983 105 1903. 2un J. A. Howard R. Sutcliffe and B. Mile. J. Chem. Soc.. Dalton Trans. 1983 1449. "' (a) A. Tiripicchio M. Tiripicchio Carnellini R. Uson L. A. Ora and Cabeza J. Organomet. Chem. 1983 244 165; (b) R. Uson L. A. Ora J. Gimeno M. A. Ciriano J. A. Cabeza A. Tiripicchio and M. Tiripicchio Carnellini J. Chem. SOC.,Dalton Trans.1983 323; (c) R. Uson L. A. Ora J. A. Cabeza C. Foces-Foces C. H. Cano and S. Garcia-Blanco J. Organomet. Chem. 1983 246 73. Cu Ag Au; Zn Cd Hg 293 Table 1 Gold heterometallic compounds Complex Structure of Cluster Re$ Au2Ru3( p-s)(co)8( PPh3)3 Au2Ru3(p-H)(pL-COMe)(C0)9(PPh3)2AuRu,( V-COM~)(CO),~(PP~~) A~Ru3(p-H)2(~3-C0Me)(C0)9(pph3) trigonal bipyramidal distorted square-pyramid butterfly metal core Ru triangle (Au edge-bridging one side) 265 265 266 266 AuRu~(~-COM~)(CO)~(PP~,) Au binds to Ru triangle making a tetrahedron two faces of 266 which have triply bridging AuPPh ligands Ru4Au(C0) 1 2(PPh3)3 bicapped trigonal-bipyramidal metal core in which two Ru,Au 267 faces of the Ru4Au fragment are capped by the other two Au atoms Ru~C(CO)I5{ p-Au(PPh,)}CI bridged butterfly configuration 268 Au atom bridges hinge bond distorted square-pyramid of Ru 268 atoms Au bridges two Ru atoms Ru5C core to which an AuPPh 269 is bound RU~C(CO)I,(NO)(AuPPh3) Ru6C core Au(PPh,) tricaps 270 three Ru atoms 0s3(c0)10( p.L-AUPEt3)2 Os3 triangle both AuPEt groups bridge same edges 27 1 ~~3(~~)8(pph3>~A~(pph3~~ Os triangle AuPPh bridges 272 (2-N HC.j H4 N) longest 0s-0s bond [OsloC(C0)24AuPPh3][PPh3Me] Au ligand adds to capping 273 tetrahedron of dianion [OS10c(c0)241~-AuIr tetrahedra 274 Au,Ir(PPh,) planar structural 274 unit WAuW is linear Au also bonds 275 to two C atoms Au sandwiched between two 228 Rh6 trigonal-prismatic units Au6 edge-shared bi-tetrahedral 277 central Au surrounded by seven 278 AuPPh moieties Au6 edge-shared bi-tetrahedral 278 diolefin = cod) have been described.281' The structure of [AuC1(C4Ph4)(phen)](6) and the preparation of related complexes have been reported.28'd The mesitylgold(1) complex (AuMes) (Mes = 2,4,6-Me3C6H2j has a five-pointed star shape.282 Dimethyl gold iodide reacts with alkali-metal amides to form Au-N 28 I (d) R.Uson J. Vicente M. T. Chicote P. G. Jones and G. M. Sheldrick J. Chem. SOC.,Dalton Trans. 1983 1131. 282 S. Gambarotta C. Flioriani A. Chiesi-Villa and C. Guastini J. Chem. SOC.,Dalton Trans. 1983 1304. 294 J. Silver heterocycles. KNH2 yields the eight-membered ring [Me2AuNH2] whereas with LiNMe2 the four-membered ring [Me2AuNMe212 is obtained.283 Reaction of halide ions with gold phenylacetylide yields the phenylethynyl gold(1) halide anion complexes [N%][XAuC,Ph] (X = CI or Br; Ph = Et; X = I; R = [Au{C5(C02Me),}(PPh,)] contains an Au(PPh,) moiety that interacts with three carbons of the C5 ring such that the co-ordination is intermediate between (T and ~7 In ~nido-[9-(q-C5H5)-p ,-(P~,PAU)~,~,~-C~N~B~H,~] .~~~ the Au bonds to two B and one P atom.286 197Au-Mossbauer parameters were reported for the salts Z[AuR2]{ R = C6F5; Z = [NBu4]+ [Ag(C,H,S)]+ [Au(SbPh3),]+ or [Au(pdma),]+ [pdma = o-phenylenebis(dimethylarsine)]}.The data for the two Au-containing cations are consistent with four co-ordination.262 Tris[bis(diphenylphosphino)methane]di-iodotetragold contains a slightly distorted Au tetrahedron one Au is co-ordinated to an iodine while the remaining Au triangle contains three identical Au environ- ments.Mossbauer spectroscopy shows the presence of both Au sites.287 Structural information of eleven Au' thiolates and twelve phosphine co-ordinated Au' thiolates has been collected.288 Gold(zzr). Kinetics of hypophosphite ion oxidation by Au"' in aqueous HCI to give phosphorus acid and Au' have been obtained and interpreted in terms of the probable formation of intermediate Au".~~~ Kinetics of the substitution of ammonia by bromide in amminetribromidogold( III) in acid solution have been Vibra-tional and 35Cl n.q.r. spectra of some trichlorochalcogen tetrachloroaurates [ACI3] 283 H. N. Adams U. Grassle W. Hiller and J.Strahle Z. Anorg. Allg. Chem. 1983 504 7. 284 0. M. Abu-Salah and A. R. Al-Ohaly Znorg. Chim. Acta 1983 77 L159. 285 M. I. Bruce J. K. Walton B. W. Skelton and A. H. White J. Chern. SOC.,Dalton Trans. 1983 809. 286 G. K. Barker N. R. Godfry M. Green H. E. Parge F. G. A. Stone and A. J. Welch J. Chem. SOC. Dalton Trans. 1983 271. 287 J. W. A. Van der Velden J. J. Bour R. Pet W. P. Bosman and J. H. Noordik Znorg. Chem. 1983 22 3112. 288 D. T. Hill B. M. Sutton A. A. Isab T. Razi P. J. Sadler J. M. Trooster and G. H. M. Calk Znorg. Chem. 1983 22 2936. 289 K. K. Sengupta B. Basu S. Sengupta and S. Nandi Polyhedron 1983 2 983. 290 L. H. Skibsted Acra Chem. Scand. Ser. A 1983 37 613. Cu,Ag Au; Zn Cd Hg 295 [AuCl,] (A = S Se or Te) indicate that the AuC1,- ion is considerably distorted from D4hsymmetry.29' Electronic absorption and m.c.d.spectra are reported for AuX,-(X = C1-or Br-) tran~-Au(CN)~X,- (X = C1- Br- or I-) and trans-Au(CN),BrY-(Y = C1-or I-) in acetonitrile Kinetics of oxidation reactions of trans- and/or cis-[PtC12(NH2R),] compounds by [AuCl,]- in the pres- ence of [NEt,Cl,] have been investigated in a~etonitrile.,~~ Reaction of tetra- bromoaurate with uridine in water occurs with a 1 1 stoicheiometry producing gold(1) and 5-brom0-6-hydroxy-5,6-dihydrouridine.~~~ The structures of cyano- and halogeno-bridged Au"' and Pd" complexes have been compared.29s Reactions of 1,3,5,-trithiane (TT) with the metal halide results in AuCI,.(TT).*~~ The structures of [AuR,(dppm)]ClO and [C1Au(dppm)Au(dppm)AuCl][AuClR3][R = C6FS; dppm = bis(diphenylphosphino)methane] have been reported the cation of the latter shows short Au-..Au contacts (ca.3.1 The He' and He" photoelectron spectra of three Au"' complexes [AuMe3L] (L = PMe3 PMe,Fh and PMePh,) have been recorded in the gas phase.298 Treatment of [Me,N][AuCl,] with di- organomercury derivatives R2Hg in which R is an ortho-nitroaryl group (R = o-O2NC6H4 or 2-Me,6-02NC6H3) gives anionic Au'" complexes of the type cis- Me4N[AuR2Cl,J. Mixed Valence Chemistry. Au'-Au" and Au'- Au"' oxidation in ylide complexes with chlorinating agents has been studied300" and a new route for the synthesis of Au' and Au" I pentafluorophenyl(y1ide) complexes rep~rted.~"' Biological Gold.Differences between the structure of the anti-arthritic Au drug Myocrisin in the solid state and in solution have been studied.301 Kinetic studies of dealkylation of ethylcobalamim by tetrachloroaurate have been reported.302 2 Zinc Cadmium and Mercury A useful review of zinc and cadmium has appeared recently.303 Zinc.-A neutron structural study of the successive phase-transitions at 60 100,235 and 300 "C in Rb2ZnC1, has provided evidence that the ZnC1 group undergoes a large libration motion304 and the structure of (NH,),ZnCl has been re-investigated to allow for twinning.304b The structures of [(C,3H27)NH3]2ZnC14 and 29 1 A. Finch P. N. Gates T. H. Page and K. B. Dillon 1.Chem. SOC.,Dalton Trans. 1983 1837. 292 H. Isci and W. R. Mason Inorg.Chem. 1983 22 2266. 293 A. Peloso J. Chem. SOC. Dalton Trans. 1983 1285. 294 R. Ettore J. Chem. Soc. Dalton Trans. 1983 2329. 295 J. A. Davies and J. F. Liebman J. Chem. SOC.,Dalton Trans. 1983 1793. 296 S. R. Wade and G. R. Willey Inorg. Chim. Acta 1983 72 201. 297 R. Ush A. Laguna M. Laguna E. Fernandez M. D. Villacampa P. G. Jones and G. M. Sheldrick J. Chem. SOC.,Dalton Trans. 1983 1679. 298 G. M. Bancroft T. C. S. Chan and R. J. Puddephatt Inorg. Chem. 1983 22 2133. 299 J. Vicente M. T. Chicote A. Arcas M. Artigao and R. Jimenez J. Organomet. Chem. 1983 247 123. 300 (a) H. Schmidbaur and P. Jandik Inorg. Chim. Acta 1983,74,97; (b) R. Uson A. Laguna M. Laguna and A. Usbn Inorg. Chim. Acta 1983,73 63. 30 I M. C. Grootveld and P.J. Sadler 1.Znorg. Biochem. 1983 19 51. 302 Y.-T. Fanchiang Inorg. Chem. 1983 22 1693. 303 E. C. Constable Coord. Chern. Rev. 1983 52 1. 304 (a) M. Quilichini and J. Pannetier Acta Crystallogr. 1983 B39 657; (b) H. van Koningsveld Acta Ciystallogr. 1983 C39. 15. 296 J. Silver [C4H6N30]2[ZnC14] have been reported.305 The synthesis and thermochemistry of adducts of Zn Cd and Hg halides with N,N-dimethylformamide have been repor- ted306 and the formation of ZnXn2-" (X- = Br- I- or NCS-) complexes in methanol studied.307 The complexes Zn(py~)~X~ and Zn(pyz)X (pyz = pyrazine; Z = C1 or Br) were doped with Mn" ions and studied by e.~.r.~O~ and the mixed ligand complexes of ZnC1 and substituted pyridines in~estigated.~" The syntheses of M(AH)2C12 (M = Zn or Cd; AH2 = l-methyl-4,4-dimercaptopiperidine) are described the AH2 group binds to Zn and Cd via one sulph~r.~" Extracts with tri-n-octylammonium chloro-complexes of Zn" of various compositions have been studied.,' Structural and spectroscopic characterization of a series of d lo metal(I1) compounds of the type [M(dmpd)X,] (M = Zn" Cd" or Hg"; dmpd = 2,2-dimethylpropane-1,3-diamine; X = C1 Br or I) have been de~cribed.~" The structures of the substituted benzylideneamine complexes [ZnBr,(C,,H 18N2)] and [ZnBr2(C13H20N2)] contain tetrahedral Zn bonding to two Br and two N Approximately octahedral Zn is found in [Zn(en),]C1,.2H203'3 and in [Zn(C4HR02)zC12] each Zn atom is in a distorted trig~nal-bipyramid.~'~ NaZn20H(S03) has been ~repared.~ In Zn(PO,), ZnO octahedra are arranged Is in and Zn2P40 I2.8H20 contains two octahedrally co-ordinated Zn atoms.316b Single crystals of KZnP,O have been grown from the ZnP03F-2.5H,0 contains both octahedral and tetrahedral Zn.316d Zn and Hg dis- solve electrolytically in the mixed non-aqueous solvents SO2-dimethylsulphoxide -dimethylformamide -acetonitrile -acetone or -nitrobenzene.I' [MFeCO,] com-plexes (M = Zn Cd or Hg) undergo mild stepwise reduction to give first the kinetically stable [M(Fe(C0),),l2- and subsequently [Fe2(C0)8]2-.317 The interaction of CO with the (1070) ZnO surface has been studied and discussed in the light of the mechanism of methanol synthesis on Zn0.318 Single crystal growth of Zn,0(B02)6 has been rep~rted.~ ZnPt306 contains Zn in a six-co-ordinate environment.320 {Zn[S(NS0)2]2}(AsF6)2.2S02is a 2D-network through 0 atoms.32I The He(1) photo- electron spectra of acetylacetone (HAA) and its Zn"(AA) complex have been mea~ured.'~~" Zn(AA)2 reacts with C2N2 in C2H4C12 or CH2C12 under ambient 305 (a) F.J. Zuhiga and G. Chapius Acta Crystallogr. 1983 839 620; (b) P. E. Bourne and M. R. Taylor Acta Crystallogr. 1983 C39 430. 306 0. A. de Oliveira A. P. Chagas and C. Airoldi Inorg. Chem. 1983 22 136. 307 H. Doe A. Shibagaki and T. Kitagawa Inorg. Chem. 1983 22 1639. 308 R. B. Birdy and M. Goodgame J. Chem. Soc. Dalton Trans. 1983 1469. 309 K. Sawada T. Sakaguchi and T. Suzuki J. Chem. Soc. Dalton Trans. 1983 447. 310 H. Barrera and F.Teixidor Polyhedron 1983 2 1165. 311 F. Cariati G. Ciani L. Menabue G. C. Pellacani G. Rassu and A. Sironi Inorg. Chem. 1983,22 1897. 312 R. Bartnik S. Lesniak A. Laurent R. Faure and H. Loiseleur Acta Crystallogr. 1983 C39 1034. 313 C. Muralikrishna C. Mahadevan S. Sastry M. Seshasayee and S. Subramanian Acta Crystallogr. 1983 C39 1630. 314 A. Boardman R. W. H. Small and 1. J. Worral Acta Crystallogr. 1983 C39 1005. 315 H. D. Lutz W. Eckers W. Buchmeier and B. Engelen 2. Anorg. Allg. Chem. 1983 499 99. 316 (a) M. T. Averbuch-Pouchot A. D. et M. Bagieu-Beucher Acta Crystallogr. 1983 C39 25; (b) M. T. Averbuch-Pouchot 2. Anorg. Allg. Chem. 1983 503 231 ;(c) L. Bohatjl and J. Liebertz Z. Kristallogr. 1983 163 251; (d) J. Durand A.Larbot L. Cot M. Duprat and F. Dabosi Z. Anorg. Allg. Chem. 1983 504 163. 317 B. A. Sosinsky R. G. Shong B. J. Fitzgerald N. Norem and C. O'Rourke Inorg. Chem. 1983,22,3124. 318 K. L. D'Amico F. R. McFeely and E. I. Solomon J. Am. Chem. SOC.,1983 105 6380. 319 L. BohatL S. Houssuhl J. Liebertz and S. Stahr 2. Kristallogr. 1983 161 157. 320 K. B. Schwartz J. B. Parise C. T. Prewitt and R. D. Shannon Acta Crystullogr. 1983 B39 217. 32 I H. W. Roesky M. Thomas J. W. Bats and H. Fuess Inorg. Chem. 1983 22. 2342. Cu Ag Au; Zn Cd Hg 297 conditions undergoing cyanation of the organometallic ring.322 Zn" triflate com- pounds containing aminopropanol isomers have been prepared.'*'' Zinc(r1) fumerate tetrahydrate contains a Zn atom surrounded by six 0 atoms.323 Di-t- butylcatecholato and semiquinonato zinc(r1) complexes have been characterized by cyclic vo1tammet1-y.~~~ and bis[l,3-bis(2- Di-aqua(4-oxoheptanedioato)zinc(11)~~~" hydroxypheny1)-1,3-propanedionato]bis(ethanol)zinc(11)~~~ contain distorted ZnO polyhedra.[M(OS,N,),][AsF,] (M = Zn or Cd) have M atoms co-ordinated by six five-membered heterocyclic ligand~.~~ [NMe4][Zn{S2P(OC6H,Me-p),l and [NEt,][Zn(S,PPh,),] both have slightly distorted tetrahedral geometries in which one S2PR2 ligand is bidentate and the other two are ~nidentate.,~' The Zn-tartarate- thiocyanate system has been investigated p~laragraphically.~~~ Complex for-mation equilibria between 2-amino-2(hydroxymethyl)propane-I ,3-diol and 1,1,1-tris(N-methylaminomethy1)ethane with Zn have been re~0rted.l~~ Dimeric methyl(dipheny1amino)zinc contains a Zn2N ring.329 Dinitrobis(pyridine)zinc(Ir) and bis(2-methylpyridine)dinitritozinc(11) have similar geometries with the amine ligands occupying cis-co-ordination sites.330 Zinc(I1) compounds of substituted imidozole ligands or benzotriazole and related ligands have been reported.'55a Zinc(rr) complexes with some bidentate ligands involving the pseudo-imidazole functional groups imidazoline benzimidazole and benzothiazole have also been de~cribed.'~~ Reactions of 2-(2-thienyl)benzothiazolinewith Zn Cd and Hg" have been reported.331 [EtZn( Et)(t-Bu)NC(H)=C(Me)6] contains a four membered Zn,02 ring.,, Ion pairing and optical activity in diastereomeric Zn"-phen S-valinate systems has been studied.333 The zinc complexes of 2-acetyl and 2-benzoylpyridine hydrazones have been characteri~ed~,~ and the Zn" Cd" and Hg" complexes of 4,6-dimethylpyrimidine-2(1 H)-one examined.335 Diamminebis( 2-sulphanil- amidopyrimidinato)zinc(11) contains Zn in a distorted tetrahedral N ~o-ordination,~~ while dichloro(terpyridyl-2:2',6':2")zinc(I I) contains pentaco-ordin- ated Zn atoms.337 Bis( N-(2-pyrrolylmethylene)-t-butylamino]zinc(11)has Zn in an elongated tetrahedral site.,,' Complexes of NN'-ethylenebis(salicy1ideneimine)with Zn Cd and Hg" have been ~haracterized.~,' The radical complex [(PhZn)L(ZnPh)]+ 322 B.Corain M. Basato A. Marcomini and H. F. Klein Inorg. Chim. Acta 1983 74 1. 323 M. P. Gupta R. D. Sahu and P.R. Maulik Z. Kristallogr. 1983 163 151. 3 24 M. E. Bodini G. Copia R. Robinson and D. T. Sawyer Znorg. Chem. 1983 22 126. 325 (a) A. Karipides Acta Crystallogr. 1983 C39 1541; (b) X. Solans M. Font-Altaba J. L. Brianso A. Llobet F. Teixidor and J. Casab6 Acta Crystallogr. 1983 C39 1512. 326 H. W. Roesky M. Thomas J. W. Bats and H. Fuess J. Chem. SOC.,Dalton Trans. 1983 1891. 327 J. A. McCleverty R. S. Z. Kowalski N. A. Bailey R. Mulvaney and D. A. O'Cleirigh J. Chem. Soc. Dalton Trans. 1983 627. 328 Km. Krishna and S. K. Jha Polyhedron 1983 2 669. 329 N. A. Bell H. M. M. Shearer and C. B. Spencer Acta Crystallogr. 1983 C39 1182. 330 M. A. Hitchman R. Thomas B. W. Skelton and A. H. White J. Chem. SOC. Dalton Trans. 1983 2273. 33 I L.F. Capitkn-Vallvey and P. Espinosa Polyhedron 1983 11 1147. 332 M. R. P. van Wet J. T. B. H. Jastrzebski G. van Koten K. Vrieze and A. L. Spek J. Organomet. Chem. 1983 251 C17. 333 A. Deciniti and G. Larrazabal Polyhedron 1983 2 1075. 334 D. Demertzi and D. Nicholls Znorg. Chim. Acta 1983 73 37. 335 R. Battistuzzi and G. Peyronel Polyhedron 1983 2 47 I. 336 N. C. Baenziger S. L. Modak and C. L. Fox jun. Acra Crystallogr. 1983 C39 1620. 337 M. Vlasse T. Rojo and D. Beltran-Porter Acta Ctystallogr. 1983 C39 560. 338 J. A. Kanters A. L. Spek R. Postma C. C. van Stein and G. van Koten Acta Crystallogr. 1983 C39 999. 339 H. A. Tajmir-Riahi Po/vhedron 1983 2 723. 298 J. Silver (L = 4,4' bipyridine) has been studied by e.s.r.and [Zn( Me,tren)dmf12' by H n.m.r. ~pectroscopy.~~' Stability constants of Zn" with 9-substituted purines have been deterrnined14'" and the extraction kinetics of zinc with alkyl-substituted dithizones Mucrocylic Complexes. Electrodes coated with poly(viny1pyridine)-co-ordinatedZn"-tetraphenylporphine (ZnTPP) have been investigated.343 Equilibrium constants have been measured for the reversible complexation of ZnTPP with poly(4-~inylpyridine) both in solution and in a system in which the polymer had been adsorbed onto fused A full pH-study of the incorporation of Zn" into uroporphyrin (I) has been reported.344 Excited-state Zn" porphyrin-quinone interactions at 10 A separation have been investigated345 and the photoredox behaviour of Zn"-porphyrins in vesiculal assemblies The synthesis of a decadendate dinucleating ligand and its aqueous equilibria with Zn" has been described"4g Zinc(1r)-sapphyrin (pentapyrrolic macrocycles) chemistry has been reported346 and the thermodynamic stabilities of Zn and Cd" complexes of a series of 0,N3-donor macrocycles Size- and structure-controlled stabilities of polyaza-crown ether complexes with Zn2' ions have been investigated as have the Zn" complexing properties of 1 -oxa-4,7,11 -triazacyclotridecane.'s2 The redox properties of (CN)&Zn a new phthalocyanine charge-transfer complex have been The synthesis of two dibenzo-3,2,3-tetramines and their Zn and Cd" complexes have been The reactions of superoxide ion with Zn and Cd" porphyrins have been studied.351 Biological Zinc.Zinc citrate contains isolated Zn" ions octahedrally co-ordinated to two equivalent ~itrates.~~~ Zinc(11) complexes of N-(2-pyridylmethy1idene)amino acids have been studied as model vitamin B6 systems.l5' Complex formation of Zn Cd and Hg with D-penicillamine has been studied using pH tit ration^.^^^ The Zn" and Co" metal ion effects on target sites of modification in metallocarboxypeptidase B have been investigated.354 X-Ray absorption spectra of native (Zn) and Co-reconstituted bovine carbonic anhydrase (CA) have been and the bicar- 340 W. Kaim J. Organomet. Chem. 1983 241 157. 34I S. F. Lincoln A. M. Hounslow and J. H. Coates Inorg. Chim. Acta 1983 77 L7. 342 H. Watarai and H. Freiser J. Am. Chem. Soc, 1983 105,189.343 (a) H. Kido and C. H.Langford J. Chem. Soc, Dalton Trans. 1983 350; (b) D. S. Becker and R. G. Hayes Znorg. Chem. 1983 22 3050. 344 A. Shamin and P. Hambright Inorg. Chem. 1983 22 694. 345 (a) J. S. Lindsey D. C. Mauzerall and H. Linschitz J. Am. Chem. Soc. 1983 105 6528; (b) K. Hurst L. Y. C. Lec and M. Gratzel J. Am. Chem. Soc. 1983 105 7048. 346 V. J. Bauer D. L. J. Clive D. Dolphin J. B. Paine 111 F. L. Harris M. M. King J. Loder S.-W. C. Wang and R.B. Woodward J. Am. Chem. Soc. 1983 105 6429. 347 K. R. Adam K. P. Dancey B. A. Harrison A. J. Leong L. F. Lindoy M. McPartlin and P. A. Tasker J. Chem. SOC., Dalton Trans. 1983 1351. 348 A. Girandeau A. Louati M. Gross J. J. Andre J. Simon C. H. Su and K. M. Kadish J. Am.Chem. Soc. 1983 105 2917. 349 C. W. G. Ansell M. McPartlin P. A. Tasker and A. Thambythurai Polyhedron 1983 2 83. 350 C. W. G. Ansell K. P. Dancey M. McPartlin P. A. Tasker and L. F. Lindoy J. Chem. SOC.,Dalton Trans. 1983 1789. 35' T. Ozawa and A. Hanaki Inorg. Chim. Acta 1983 80 33. 352 R. Swanson W. H. Ilsley and A. G. Stanislowski J. Inorg. Biochern. 1983 18 187. 353 R. Strand W. Lund and J. Aaseth J. Inorg. Biochem. 1983 19 301. 354 N.Zisapel T.Blank and M. Sokolovsky 1.Inorg. Biochern. 1983 18 253. 355 (a) V. Yachandra L. Powers and T. G. Sprio J. Am. Chem. Soc. 1983 105 6596; (6) Y. Pocker and T. L. Deits J. Am. Chem. SOC.,1983 105. 980. Cu Ag Au; Zn Cd Hg 299 bonate proton in CA catalysis has been studied.3cch A quarternary Zn complex involving pyridoxamine glycine and ethylenediamine has been described.'06L1 Hexa- aqua-zinc(I 1)bis(2,6-dihydroxybenzoate)dihydrate has been reported as a humic-like model.") Tetrakis(3,5 -di -t -bu ty1-4- hydro xyphe n yI )porp h yri n and its Zn I ' derivative have been studied as models for per~xidases.~~~ The pH dependency of the kinetics of Zn carboxypeptidase-catalysed enolization of a substituted propionic acid has been determined.357 67Zn N.m.r.studies of aqueous Zn*+ Zn2'-insulin complexes and other Zn7+ ligand complexes have been reported. Cadmium.-The structures of many polytypes of Cdl? have been Cd&aCI,.8.5H20 crystals show a persistent occurrence of twinning by pseudosym- met~y.~~" [CdCI,(C,H,(OH)2)]7.C2H4(OH)2contains Cd(C2H,02)CI,,2 octahedra with two edges (CI double bridges) in common which form endless chains.36' 2-amino-4,5-dihydro-3H -1,3-thiazolium trichlorocadmate( I I) is polymeric in struc- ture and consists of ATH+ and CdCI,- anions.The Cd atoms are octahedrally co-ordinated and linked into infinite chains by double CI catena-Di-p-chloro-iodo(I H '-S-methylisothiocarbonohydrazidium-N)cadmium( I I) contains Cd in slightly distorted octahedral co-ordination.'" CdPt'O contains edged-shared PtO octahedra in chains and columnar stacks of planar PtO groups.364 In Cd,Na(VO& CdO octahedra form infinite edge-sharing chains linked by corner- sharing VO and Cd/ NaO tetrahedra.jb5 Cd(SCH2C02Et) contains [Cd(p-SCH2C02Et)2] linear chains along which Cd atoms tetrahedral CdS, and dodecahedra1 CdS,O co-ordinations altenate.365 The growth of mixed crystals of CdS,-,Se has been described.367 Spectra have been reported for the surface- adsorbed free radical anion of methylviologan (MV+') formed from MV' by electron transfer from colloidal CdS particles following photoexcitation by continuous wave Raman lasers.3h8 KCd(N3)?.H20 and K2Cd(N,) both contain Cd surrounded by six azide groups.3hy Cd-thiocyanate-thioacetamide and Cd-thioacetamide-nicotinamide systems have been studied and many mixed complexes detected.37" I13 Cd n.m.r. studies and crystal structure determinations of bis( p-o-hydroxyben- zoato)bis(o-hydroxybenzoat0)tetra-aquodicadmium(I I) and tris(pyridine)bis(o-hydroxybenzoato)cadmium(lr) confirm pentagonal-bipyramidal seven-co-ordinate Cd" .37' An approximately tetrahedral CdS moiety has been found in tetrakis(N,N'-dimethylthiourea-S)-cadmium( 11) nitrate."2 In Cd( NCS)2( 1,2,4-tria~oIe)~ the Cd2+ 356 T.G. Taylor K. B. Nolan and R. Hildreth J. Am. C'hem. Soc. 1983 105 6149. 757 T. E. Spratt T. Sugimoto and E. T. Kaiser J. Am. Chem. Soc. 1983 105 3679. 358 (a)T. Shimizu and M. Hatano Inorg. C'him. Acfa 1983 76 L177; (b) M. Kodaka T. Shimizu and M. Hatano Inorg. C'him.Acrn. 1983 78 L55. 359 (a) B. Palosz Acra ('rysrallogr. 1983 C39 1160; (b) S. K. Chaudhary G. K. Chadhu and G. C. Trigunayat Acra Crystallogr. 1983 C39 675. 360 H. Leligny and J. C. Monier Acra Crystallogr. 1983 839 427. 36 I F. A. Schroder J. W. Bats H. Fuess and E. J. Zehnder Z.Anorg. Allg. Chem. 1983 499 181. 362 M. Kubiak T. Glowiak and H. Kozlowski Acra Cryrfallogr. 1983 C39 1937. 36? F. Bigoli M. Lanfranchi E. Leporati and M. A. Pellinghelli Acta Crystallogr. 1983 C39 1333. 364 C. T. Prewitt K. B. Schwartz and R. D. Shannon ACIUCrysfallogr. 1983 C39 519. 365 S. C. Abrahams P. Marsh and J. Ravez Acra Crysfallogr. 1983 C39 680. 366 I. G. Dance M. L. Scudder and R. Secomb Inorg. Chem. 1983 22 1794. 367 B. A. Kazennov and V. F. Chernysheva Soc. fhys. Cry~fallogr.,1983 28 242. 36X K. Metcalfe and R. E. Hester J. ('hem. Soc. C'hem. Commun. 1983 133. 369 W. Clegg H. Krischner A. I. Saracoglu and G. M. Sheldrick Z. Krisrallogr. 1983 161 307. 37(1 V. G. Dongre. Inorg. Chim. Acfa 1983 73 281. 37 I N.G. C'harles E. A. H. Griffith P. C.. Rodesiler. and t.L. Amma. Inorg. ('him.Acta. 1983 22 2717. 372 P. F. Rodesiler. N. G. Charles. E. A. H. Grifith. and C... L. Amma. Am Crvrtallogr. 1983 C39. 1350. 300 J. Silver is octahedrally co-ordinated to two monodentate N-bonded 1,2,4-triazole ligands two thiocyanate N atoms and two thiocyanate S atoms.373 The stereochemistry of [C~~(SC~H~),O]~-, a cage complex related to the Cd- cysteinate aggregates in metallothioneins has been The essential structure is shown (7). A correlation of u.v. c.d. and '13Cd n.m.r. data and a '13Cd n.m.r. characterization of the binding sites in the reconstituted protein has been reported.375 [Cd4(SPh&,12-S Mercury.-A review with 176 references spanning the years 1980-198 1 has appeared.376 Two complexes of thiamine [ThH] with HgC12-[ThH]"[HgCl,]~ and [ThH]2+[HgC14]2-have been prepared the latter contains tetrachloromercurate ions.377 In [NH3(C2H5)]2[HgCl,] there is a two-dimensional [HgC14]2,"- layer made up of HgCl 0~tahedx-a~~' and 1,4-diazabicycl0[2.2.2]octan-1,4-diium HgC14.H20 contains regular HgC142- tetrahedra.379 HgClz has been used in the chemical trans- port of Ti,,02,- phases.380 Correlations between crystal structures and vibrational spectra of complexes HgX2(PR3) (where X = C1 Br or I and R = Ph; R = 1,2,5-triphenylphospholeand X = C1 or Br; R = cyclohexyl Me or Et and X = C1; R = Me and X = Br) have been rep~rted.~'' Reactions of carbonyl complexes (NN)(Ph,P)M(CO) (M = Mo or W; NN = biby or phen) with HgX2 (X = C1 CN or SCN) involve either partial halogen displacement to yield HgX complexes or retention of both halogens to give addu~ts.,'~ In (urea)HgCl each Hg atom is 373 J.G. Haasnoot G. C. M. de Keyzer and G. C. Verschoor Acta Crysrallogr. 1983 C39 1207. 374 K. S. Hagen and R. H. Holm Inorg. Chem. 1983 22 3171. 375 P. A. W. Dean A. Y. C. Law J. A. Szymanska and M. J. Stillman Inorg. Chim. Acta 1983 78 275. 376 E. C. Constable Coord. Chem. Rev. 1983 52 53. 377 N. Hadjihadis A. Yannopoulos and R. Bau Inorg. Chim. Acta 1983 69 109. 378 B. Salah A. Daoud G. Constant J. Jaud and J. Galy Acta Crystallogr. 1983 C39 63. 379 L. Book and T. C. W. Mak Inorg. Chim.Acta 1983 77 L57. 380 F. J. Seiwert and R. Gruen 2.Anorg. Alfg. Chem. 1983 503 151.381 (a) N.A. Bell M. Goldstein T. Jones and 1. W. Nowell Inorg. Chim. Acta 1983 69 155; (b) N. A. Bell T. D. Dee M. Goldstein P. J. McKenna and I. W. Nowell Inorg. Chim. Am 1983 71 135; (c) N. A. Bell M. Goldstein T. Jones and I. W. Nowell Inorg. Chim. Acta 1983 75 21. 3a2 M. P. Pardo and M. Cano. J. Organomet. Chem. 1983 247 293. Cu Ag Au; Zn,Cd Hg 30 1 essentially in the form of a discrete HgC1 molecule.383 U.V. and IH I3C and 19Hg n.m.r. spectra of CH4-,,(HgX) (X = C1 Br I or CN) have been reported.384 The compounds of tetrathiotetracene and tetraselenotetracene with hexabromodimercur- ate dianion contain centrosymmetric (HgzBr6)'- dimers ;385 similar dimers are found in [Mg(OH2)6][Hg,X6] (X = Br or I),385b and in MgHg3C18.6H20.385' Free-radical chain-substitution reactions of alkymercury halides have been discussed386 and force constants of [Hg(CF,),] [Hg(CCl,),] [Hg(CF,)X] (X = C1 Br or I) and [Hg(CCl,)X] (X = C1 or Br) calculated.3s7 In [OHg3CCHO]N03.H20,388 the geometry is defined by a flat Hg30 oxonium pyramid and a Hg3CC tetrahedron.Hg302(N03) is built up of two Hg302 honey- comb nets and of isolated NO3 Ethylphosphinediacetic acid is a new ligand that is highly selective for soft metals such as Hg.389 c~Mn(C0)~ reacts with excess Hg(OCOCF3) to generate (C0)3MnC,(HgOCOF3),.390 A number of organomercury derivatives of arylazobenzoic acids have been prepared391 and com- plexes of the type C(HgX),) (X = CN- HCO, CH,CO, and CF3C0y) studied by i.r. and Raman spectroscopy.392 Tetramethylammonium tetrakis(4-chloroben- zenethiolato)mercury(rr) contains the [Hg(SC6H4C1)4]2- complex anions.393 The n- and i-propyl mercury selenocyanates have been reacted with thiocyanates of Co" and Ni" to form (SCN),M(NCSeHgR) [M = Co" or Ni"; R = n-propyl or i- pr~pyl].~~~ Zn Cd and Hg complexes of the substituted pyrimidine (dmtp) have been reported; the structures of Cd(NCS)2(dmtp)2(H20)2 and Hg(SCN),(dmtp) have been solved the latter contains Hg in a distorted tetrahedral ~o-ordination.~~' 31P and '99Hg n.m.r.measurements have been reported for cationic Hg ph~sphite,~~~" anionic phosphito-P-Hg complexes,396b and compounds involving (Hg- P) ten-membered rings.396c Hg4(AsF6) contains almost linear Hg,,+ ions and octahedral AsF,- ions.397 Reaction of trifluoromethyl radicals with dimethylmercury generated bis(tri- fluoromethyl)mercury.398Organomercury( 11) derivatives of 2-thiouracil have been 383 K.Lewinski J. Sliwinski and L. Lebioda Inorg. Chern. 1983 22 2339. 384 (a) D. K. Breitinger W. Kress R. Sendelbeck and K. Ishiwada J. Organornet. Chern. 1983 243 245; (6) W. Kress D. K. Breitinger and R. Sendelbeck J. Organornet.Chern. 1983,246 1 ;(c) D. K. Breitinger and W. Kress J. Organornet. Chern. 1983 256 217. 385 (a) R. P. Shibaeva and V. F. Kaminski Sou. Phys. Crystallogr. 1983 28 173; (b) K. Brodersen G. Pezzei and G. Thiele Z. Anorg. Allg. Chern. 1983,502 209; (c) K. Brodersen G. Pezzei and G. Thiele Z. Anorg. Allg. Chern. 1983 499 169. 386 G. A. Russell and H.Tashtoush J. Am. Chern. Soc. 1983 105 1398. 387 J. Mink and P. L. Goggin J. Organornet. Chern. 1983 246 115. 388 (a) D. Grdenic M. Sikirica D. MatkoviC-CalogoviC and A. Nagl J. Organornet. Chern. 1983 253 283 ; (6) H. Behm Acta Crystallogr. 1983 C39 1319. 389 D. Noskova and J. Podlahova Polyhedron 1983 2 349. 390 L. G. Kuzimina A. G. Ginzburg Yu. T. Struchkov and D. N. Kursanov 1.Organornet. Chern. 1983 253 329. 39 I K. K. Sarkar T. K. Chattopadhyay and B. Majee Polyhedron 1983 2 493. 392 J. Mink Z. Meic M. Gal and B. Korpar-Colig J. Organornet. Chern. 1983 256 203. 393 S. Choudhury I. G. Dance P. J. Guerney and A. D. Rae Inorg. Chirn. Acta 1983 70 227. 394 P. P. Singh and V. P. Singh Znorg. Chirn.Acta 1983 71 205. 395 J.Dillen A. T. H. Lenstra J. G. Haasnoot and J. Reedijk Polyhedron 1983 2 195. 396 (a) P.-P. Winkler and P. Peringer Znorg. Chirn. Acta 1983 76 59; (b) P. Peringer and D. Obendorf Znorg. Chirn.Acta 1983,77 L147; (c) P. Peringer and J. Eichbichler J. Organornet. Chern. 1983,241,281. 397 B. D. Cutforth R. J. Gillespie P. Ireland J. F. Sawyer and P. K. Ummat Inorg. Chern. 1983 22 1344. 398 M. Guerra R. L. Armstrong W. J. Bailey jun. and R. J. Lagow J. Organornef. Chern. 1983 254 53. 302 J. Silver reported.399 A 199Hg n.m.r. study of some silylmercury derivatives and selected organomercury compounds has been pre~ented.~~ Reactions of Mo(CO),DAB (DAB = diacetyldihydrazone) and Mo(CO)~-(PPh3)*DAB with HgX (X = C1 I or SCN) have been st~died.~" Hg(CN)- { truns-Mo(CO),(AsMe2Ph)( q5-C5Hs)} contains an Hg-Mo bond length of 2.65 A which is the shortest yet Reaction of perfluor-n-propyliron tetracarbonyl iodide with mercury compounds yields [C3F7Fe(C0)4]2Hg and C3F7Fe(C0)4HgC3F7.403 The structures of (p-MeHgS),Fe2(NO) and (p-MeHgS)2Fe2(C0)6 have been solved.404 Hg[Ru3(C0),(C2-t-Bu)1 and [(C2-t-Bu)Ru,(CO),HgMo( .I)-C,H,)(CO),] contain Hg-bridged metal clusters in the latter the Hg cation bridges one side of the triangular Ru cluster and also bonds to the Mo atom.405 [{CON(CH,CH,PP~,)~]}~( p-Hgz].thf contains a Co-Hg-Hg-Co linear Trimetallic complexes of [IrC1(SnC13)( HgCl)(CO)(PR),] have been studied by 31P l19Sn and I9,Hg n.m.r.407 Ir-Hg bonds have been found in [(PPh3),(CO)Cl,IrHgR] (R = c6Cl, C2cl3 or C6H3C12) complexes.408 [(C6F,)3Ge]3Hg and (Ph3P),Ni react to give (Ph3P)2Ni[Ge(C6F5)3]HgGe(C6F5)3 which contains a Ge- Ni-Ge chain.409 The complexes [Pd3(C0)3(PEt)3]2Hg and Pd4(CO),(PEt3)4(HgBr)2 have been prepared the latter consists of two Pd3Hg tetrahedra with a common Pd-Pd edge.410 The synthesis of a number of Hg-Pt acetylides of the type (RCEC),Pt( p-dppm)2HgC12 (R = C&Me-p Ph Me or Pr") have been rep~rted.~' I The Rh-catalysed decomposition of hydroxymercurated ethylene to ethanol and acetate has been reported4I2 and reduction and exchange reactions of Hg" phosphine complexes at Hg electrodes in dichloromethane have been studied.413 Biological Mercury.A "N and 199Hg n.m.r. investigation of inosine protonation and diamagnetic Hg2+ (and Zn2') ion complexation supports the notion that the binding of the first equivalent of Hg2+ is site selective (at the N-7 A number of studies of Me"-complexes have appeared,,I5 including complexes with thiol and 399 G.C. Stocco A. Tarnburello and M. A. Girasolo Inorg. Chim.Acta 1983 78 57. 400 M. J. Albright T. F. Schaaf A. K. Hovland. and J. P. Oliver J. Organomet. Chem. 1983. 259. 37. 401 M. Iglesias A. Llorente C. Del Pino and A. Santos J. Organomet. Chem. 1983 256 75. 402 G. Salem B. W. Skelton A. H. White and S. B. Wild J. Chem. Soc. Dalton Trans. 1983 21 17. 403 I. I. Gueros and Yu. L. Yagupolskii J. Organomet. Chem. 1983 247 81. 404 T. C. W. Mak L. Book C. Chieh M. K. Gallagher L. C. Song and D. Seyferth Inorg. Chim. Acta 1983 73 159. 405 S.Errner K. King K. I. Hardcastle E. Rosenberg A. M. Manotti Lanfredi A. Tiripicchio and M. T. Carnellini Inorg. Chem. 1983 22 1339. 406 F. Cecconi G. A. Ghilardi S. Midollini and S. Moneti J. Chem. SOC.,Dalton Trans. 1983 349. 407 M. Kretschrner P. S. Pregosin P. Favre and C. W. Schlaepfer J. Organomet. Chem. 1983 253 17. 408 0. Rossell and M. Seco Inorg. Chim.Actu 1983 74 119. 409 L. S. Isaeva L. N. Morozova V. V. Bashilov P. V. Petrovskii V. 1. Sokolov and 0.A. Reutov J. Orgunomet. Chem. 1983 243 253. 410 (a) E. G. Mednikov N. K. Erernenko V. V. Basilov and V. 1. Sokolov Inorg. Chim.Acta 1983 76 L31; (6) E. G. Mednikov V. V. Basilov V. I. Sokolov Yu. L. Slovokhotov and Yu. T. Struchkov Polyhedron 1983 2 141. 41 I C. R. Landrik D.M. McEwan P. G. Pringle and B. L. Shaw J. Chem. SOC.,Dalton Trans. 1983 2487. 412 J. Cook and P. M. Maitlis J. Chem. Soc. Dalton Trans. 1983,?319. 413 A. M. Bond R.Colton D. Dakternieks K.W. Hank and M. Svestka Inorg. Chem. 1983 22 236. 414 G. W. Buchanan and M. J. Bell Can. J. Chem. 1983,61 2445. 415 (a) A. J. Carty S. F. Malone N. J. Taylor and A. J. Canty J. Inorg. Biochem. 1983 18 291; (6) A. J. Canty A. J. Carty and S. F. Malone J. Inorg. Eiochern. 1983 19 133; (c) A. P. Arnold A. J. Canty P. W. Moors and G. B. Deacon J. Inorg. Biochem. 1983. 19 319. Cu Ag Au; Zn,Cd Hg dithiol antidotes selonates and amino acids. The removal of (MeHg") from its glutathione and haemoglobin complexes in haemolysed erythrocytes has been studied by 'Hn.m.r.D. L. Robenstein R. S. Reid and A. A. Isab J. Inorg. Biochem. 1983 18 241.

ISSN:0260-1818    

DOI:10.1039/IC9838000275

出版商:RSC    

年代:1983

数据来源: RSC

摘要:

12 Sc Y the Lanthanides and the Actinides By S. J. LYLE The Chemical Laboratory University of Kent at Canterbury Kent CT2 7NH 1 Introduction The report on these elements follows a plan similar to that adopted last year. As in the previous year research output on compounds of Y and the lanthanides (Ln) represent a major fraction of the total for the title elements with continuing emphasis on the hydrides mixed valence chalcogenides and complexes with organic ligands. Again there is evidence for a wide range of developments including organometallic studies in the chemistry of a few actinides (An),particularly U Th and Pu. 2 Scandium The first successful study on the metal involving de Hass-van Alphen measurements has been reported and a band structure proposed’ to account for the results.It has been established’ from a matrix isolation study of the X-band e.s.r. spectrum of 45Sc2 in Ne and At matrices at 4 K that the ground state of Sc2 is ’X.The hyperfine parameters are in essential agreement with a so’da’dn2 electronic configuration. From a neutron diffraction study of 2H in a single crystal of SC’H,,,~ it has been deduced that the H atom occupies tetrahedral sites in the host lattice a conclusion at variance with an earlier n.m.r. study.3 The magnetic susceptibility of the a-phase in the Sc-H system decreases with increasing temperature (4.2K to ambient) and with increasing hydrogen concentration. However the Fermi level appears to remain with the The ground state of ScF is predicted5 to have ‘X+symmetry with a bond length of 1.8118 (exptl.1.787) and a vibration frequency of 742.3 cm-’ (exptl. 735.6). The bonding is ionic and corresponds to Sc+F-. On the other hand it was found from theoretical considerations that for ScLi the states which correlate with the 4s23d’configuration of Sc (‘,,X+ ‘*,A) are weakly bound (<6kcal mol-’) and lie close to each other precluding an assignment based on ground-state calculations. Differences between ScLi and ScH and similarities with Sc2 were noted in discussion.6 Transport growth of ScF has been studied’ in the presence of MC14 (M = Si or ’ J. E. Schirber A. C. Switendick and F. A. Schmidt Phys. Rev. 8 Condens. Matter 1983 27 6475. ’L. B. Knight jun. R. J. van Zee and W. Weltner jun. Chem. Phys. Lett. 1983 94 296.’ C. K. Saw B. J. Beaudry and C. Stassis Phys. Rev. B Condens. Matter 1983 27 7013. N. V. Volkenshtein E. V. Galoshina M. E. Kost and T. S. Shubina Phys. Status Sofidi,1983 B117,K47. J. F. Harrison J. Phys. Chem. 1983 87 1312. J. F. Hamson 1.phys. Chem 1983 87 1323. ’ W. Redlich and T. Petzel Rev. Chim. Miner. 1983 20 54. 305 306 S. J. Lyle Ge). Transport appears to be based on reactions 1 and 2. 4ScF3(s) + 3MC14(g) 4ScCl3(g) + 3MF4(g) and 4ScF,(s) + 3MC14(g) 2Sc,Cl,(g) + 3MF4(g) The literature on ScO has been reviewed' and Franck-Condon Factors y-centroids and a new set of constants reported for the B-X transition that correlate with observed spectral intensities and band origins. So vacancy ordering in slowly cooled Sc,-,S has been examined by high resolution electron microscopy.In addition to previously observed vacancy segregation into alternate (1 11) planes of the NaCl substructure a further incommensurate ordering of the vacancies within (1 1 plane; was revealed; this latter type of ordering was easily destroyed by the electron beam. Mixtures of SmS and ScS form solid solutions Sm,-,Sc,S for x < 0.4 in which the divalent configuration of the Sm is probably maintained." Mixed metal silicides are currently of interest as superconductors. Low tem- perature heat capacities of M2Fe3Si5(M = Sc Y or Lu) have been determined revealing several anomalous properties of the superconducting state; the results show a large linear term in the heat capacity and a reduced normalized jump in specific heat at the critical temperatures." The crystal structure of Sc3NiSi3 has been determined and shown to consist of SiSc,Ni and SiSc trigonal prisms.'' Sc2FeSi2 crystals also belongi3 to this system while Sc3Ni Si4 crystals are hexagonal with Sc forming triangular clusters having 32 neighbouring Ni and Si atoms; the structure is closely related to that of EuMg,.I4 The structures of MSc(SO,) (M = Cs Rb or K) were studied at high tem- peratures and the M2S04-Sc2( phase diagram determined.15 Three phases (a,p and y) have been recognized in the ferroelectric ionic conductor N~,SC,(PO~)~; they interconvert at 313 K (ae6) and 393 K (6 y).The phase transitions have been considered in structural terms and it is concluded that the Na+ conduction channels strongly reflect the phase structures.l6 On heating Sc(H2P04) decomposes at or above 543 K to give ScH2P3OI0; the purest ScH2P3OIo is obtained by heating at 623 K for 16 h.At temperatures between 673 K and 1013 K and [Sc( P03),ln are formed.I7 Sc( Re0& decomposes on heating in vucuo to Sc203 and Re207 without production of gaseous Re-containing compounds of SC.'* A study of the hydrolysis of Sc3+ in 0.1 M KN03 at 25 "C by potentiometry is consistent with formation of ScOH2+ Sc,(OH):+ and Sc,(OH)Z+ for each of which * C. B. SuPrez Physica B + C (Amsterdam) 1983 121 295. H. F. Franzen R. T. Tuenge and L. Eyring J. Solid State Chem. 1983 49 206. R. B. Beeken J. Less-Common Met. 1983 94 161. 10 'I C. B. Vining R.N. Shelton H. F. Brown and M. Pelizzone Phys. Rev. B Condens. Matter 1983 27 2800. 12 B. Ya. Kotur and E. I. Gladyshevskii Kristallograjiya 1983 28 461. l3 B. Ya. Kotur and M. Sikiritsa Kristaffograjiya 1983 28 798. 14 B. Ya. Kotur M. Sikiritsa 0. I. Bodak and E. I. Gladyshevskii Kristallograjyu 1983 28 658. Is F. M. Korytnaya S. N. Putilin and A. N. Pokrovskii Zh. Neorg. Khim. 1983 28 1716. 16 V. B. Kalinin B. I. Lazoryak and S. Yu. Stefanovich Kristallograjiya 1983 28 264. " 2.Kanepe and Z. Konstants Zzv. Akad. Nauk SSSR Neorg. Mater. 1983 19 969. K. V. Ovchinnikov E. N. Nikolaev and G.A. Semenov Zh. Obshch. Khim. 1983,53,966 (Chem.Abstr. 1983 99 62032). Sc Y the Lanthanides and the Actinides 307 formation constants have been computed.” The composition and structure of the co-ordination spheres of aqueous solutions of Sc3+ and La3+ have been examined2’ by 46Sc and ‘39La n.m.r.respectively. Both were considered to form inner sphere complexes with NO and ClO but while C1- co-ordinates readily with Sc3+ it only does so with La3+ for [Cl-1 [La”] > 17.6 at 0.4g l-’La3+. Sc3+ complexation with Arsenazo I11 (disodium 2,7-bis( 2-arsenopheny1azo)- 1,8-dihydroxynaphthalene-3,6-disulphonate) has been studied by stopped-flow spectrophotometry at pH 0.5 to 0.9 p = 0.5(NaC104) and 25°C. The reaction is first order for [Sc3+] and [Arsenazo 1111 and inverse first order for [H+]. The rate determining step is 1 1 complex formation.21 3 Yttrium and the Lanthanides Papers presented at the 16th Rare Earth Research Conference held in April 1983 at Tallahassee Florida have been published in vols.93 and 94 of the Journal of Less-Common Metals. The Proceedings of the NATO Summer School held at Braunlage W. Germany in July 1982 have been published recently.22 The publication contains useful contributions from invited lecturers who have reviewed the literature and put developments in the various areas into perspective. The IUPAC Commission on Equilibrium Data has published a volume on the solubility of nitrates of Sc Y and Ln. Binary and multicomponent systems in aqueous and non-aqueous solvents are evaluated but molten state systems are excluded.23 The re~ommended~~ atomic weight of Lu is now 174.967 and the intrinsic quad- rupole moment of 176Lu is 6.98 * 0.10 b.25 Magnetic structures of the Ln metals have been reviewed.26 From a consideration of energy variations related to changes in the 4f orbital populations electron affinities Ln + e + Ln- are predicted; they lie in the range +0.5 to -0.3 eV.27 The 4f orbital is highly localized in all lanthanides except Ce where the degree of localization is reduced so that the wave function can mix with extended states of a solid.The 4f character is localized in hydrides and chalcogenides slightly delocalized in the pnictides and more nearly band-like in some intermetallic compounds.28 It has been pointed out that the Judd-Ofelt intensity model for 4f + 4f transitions is inadequate for representation of effects due to optical anisotropic ligand dipolar polarizations.Extra intensity parameters are needed when lanthanide-ligand pairwise interactions are not cylindrically symmetric.29 l9 P. L. Brown J. Ellis and R. L. Sylva J. Chem. SOC.,Dalton Trans. 1983 35. 20 V. P. Tarasov G. A. Kirakosyan S. V. Trots Yu. A. Buslaev and V. T. Panyushkin Koord. Khim. 1983 9 205. 2’ H. Mogi T. Odashima and H. Ishii Nippon Kagaku Kaishi 1983,1437 (Chem. Abstr. 1983,99,182284). 22 ‘Systematics and Properties of the Lanthanides’ ed. S. P. Sinha D. Reidel Publ. Co. Dordrecht Netherlands 1983. 23 ‘IUPAC Commission on Equilibrium Data. Solubility Data Series vol. 13 Scandium Yttrium Lan- thanum and Lanthanide Nitrates’ ed. S. Siekierski T. Mioduski and M. Salomon Pergamon Press Oxford 1983. 24 N. E.Holden and R. L. Martin Pure Appl. Chem. 1983 55 1101. 25 J. Gerl K. Ronge V. Ramaniah T. W. Elze A. Hanser and L. D. Tolsma 2. Phys. A. 1983,310 349. 26 W. C. Koehler J. Less-Common Met. 1983 93 15. 21 S. G. Bratsch Chem. Phys. Lett. 1983 98 113. 28 J. H. Weaver J. Less-Common Met. 1983 94 17. 29 M. F. Reid and R. S. Richardson Chem. Phys. Left. 1983 95 501. 308 S. J. Lyle Lattice and Schottky contributions to the morphology of lanthanide heat capacities have been reviewed3' and thermodynamic properties (Cp G H and S) for Dy have been evaluated from data in the 7 to 300 K range.,' A set of standard electrode potentials (Ln3+ + 3e + Ln) have been p~blished.~ The origins and rationalization of intra-row periodicity in the Ln series of compounds (tetrad and double-double effects) have received renewed interest and provide subject matter for several papers.33-35 Interest continues in hydrides of individual lanthanides and of lanthanide alloys.Occupation of tetrahedral and octahedral holes in Ln by H has been reviewed as a probe for the elucidation of electronic structure.36 A new method has been described for the preparation of hydrides with high H content. Gas from AlH or MgH is used under high pressure; when AlH was used SmH2,95 was obtained under 4 GPa at 300°C in 30mi11.~~ Single crystals of YbH1.75 were grown for the first time in sealed tungsten crucibles.38 Tetrahedral holes in hcpTm are preferably filled by 2H in the formation of a-Tm2Ho,06 from room temperature to 4.2 K.Both magnetic moment and a-Tm2Ho,09 and Nee1 temperature decrease with increasing 2H content consistent with depopula- tion of metallic d-bands decreasing the number of conduction electrons responsible for the RKKY exchange intera~tion.~~ Most of the work on binary hydrides centres around dihydride formation. The 4f electron densities in CeH2. and CeH2.4 were compared with those in CeA12 CePd, CeRh, and CeRu2 and in analogous lan- thanide compounds by photoelectron spectroscopy. Contrary to expectation no evidence was found for change in 4f occupation across the series LaH,, to CeRu (reportedly 4f0). The apparent valency changes are ascribed to hybridization effects in accord with recent band-structure calculations?0 A magnetic susceptibility study of SmH revealed an anomaly at 9 K attributable to antiferromagnetic ordering.41 A neutron-diff raction study has shown that YbH2 and Yb2H2 are isostructural with the hydrides of alkaline earths at 300 K and atmospheric pressure.42 The orthorhom- bic and cubic crystal forms of YbH1.94 and YbH2.56 respectively represent the only two phases formed by Yb at 250 to 800 "C and 0 to 120 atm.H,; a metastable cubic phase YbH2.02 reported previously was not detected.38 Yb2H1,98 crystallizes in the orthorhombic system with the PbCl,-type structure.43 EuH, the highest hydride of Eu prepared from the elements at 500 "C has been described as a new ferromagnetic semiconductor.4 Magnetic susceptibility data reveal distinct anomalies at 4.2 and 30 E. F.Westrum jun. J. Chem. Thermodyn. 1983 15 305. 3' E. B. Amitin W. G. Bessergenev Yu. A. Kovalevskaya and I. E. Paukov J. Chem. Thermodyn. 1983 15 181. 32 V. N. Korshunov Electrokhirniyu 1983 19 346. 33 V. I. Spitsyn V. G. Vokhmin and G. V. Ionova Zh. Neorg. Khim. 1983 28 819. 34 B. F. Druzhinskii Zh. Neorg. Khim. 1983 28 1091. 35 V. I. Spitsyn V. G. Vokhmin and G. V. Ionova Zh. Neorg. Khim. 1983 28 1638. 36 J. Hauck J. Less-Common Met. 1983 94 123. 37 K. Wakamori S. M. Filipek and A. Sawaoka Rev. Sci. Instrum. 1983,54 1410. 38 R. Bischof E. Kaldis and I. Lacis J. Less-Common Met. 1983 94,117. 39 J. N. Daou P. Radhakrishna P. Vajda and Y. Allah J. Phys. F. 1983 13 1093. 40 D. J. Peterman J. H. Weaver M. Croft and D. T. Peterson Phys.Rev. B Condens. Mutter 1983,27,808. 41 0. J. Zogal Phys. Status Solidi B 1983 117 717. B. Lebech N. H. Andersen S. Steenstrup and A. S. Pedersen Acta Crystullogr. Sect. C. Cryst. Str. 42 Commun. 1983 C39 1475. 43 P. Fischer J. Schefer K. Tichy R. Bischof and E. Kaldis J. Less-Common Met. 1983 94 151. 44 R. Bischof E. Kaldis and P. Wachter J. Mugn. Mugn. Muter. 1983 31-34 255. Sc Y the Lanthanides and the Actinides 309 2.4 K for CeH2.43 and CeH3,00 respectively. CeH2.43 orders ferromagnetically whereas CeH,,, exhibits an antiferromagnetic alignment along the (1 11) directi01-1.~~ Heat capacity values in the range 1.2 to 300 K for La2H3 show sharp anomalies in La2H at 21 1,230.5,233.5 and 274 K and in LaH at 241 and 270 K.The lowest transition in each is thought to be a semiconductor to metal transition.& Of the binary metal systems LaNi is most widely studied. In addition to hydrogen storage and energy conversion it has been examined for the separation of H2 from gas mixtures and as a hydrogenation catalyst. Selective removal of H2 from its mixture with N2 CH4 COz CO or H2S has been investigated by cyclic absorption- desorption steps. N2 or CH4 (each ~20 vol.%) do not affect rates of absorption but C02 (G20 wt.%) passivates LaNi,; CO at <1 vol.O/~ deactivates the alloy and H2S causes strong attenuation which however can be removed by heating at 700 K.47 O2 as a minor constituent can impair H2 absorption probably by surface oxidation but addition of Al to the alloying mixture improves tolerance?* LaNi has been examined also for the recovery of H2 from the purge gas in a NH manufacturing plant49 and for separation of H2-NH3 mixture^.^' The alloy can be prepared by the reduction of La203 + NiO with CaH2 in H2 at high temperatures; the product is thought to have a surface layer of Ni but the bulk structure of LaNi and it is claimed to have greater catalytic activity for C2H4 conversion into C2H6 than that prepared by the metallurgical process.51 Rates of absorption-desorption of H indi- cate that the processes are complicated with rate determining steps dependent on conditions.Over a wide range of pressures of H2 at 60 to 65 "C the hydriding rate is under the mixed control of a surface process and a bulk solid process (probably diffusion) which can become rate determining at lower temperatures and at high pressures.Dehydriding appears to be rate limited by a surface process.52 H-Mobility in the solid appears to be high; from neutron-diffraction it has been deduced that LaNi 2H6 is hexagonal with H distributed over one fully and another partly occupied interstitial site with H in the latter having high local mobility.53 Other alloys of composition LnM (M = 3d-block element) are of relatively minor interest but it has been noted that on exposure of LaCoH to 02,water formation is catalysed by the solid phase with an essentially linear dependence of rate on x.,~ From a studys5 of reactions of atomic and molecular F on Gd it was deduced that a non-volatile ,non-passivating fluoride GdF (x < 3) of high m.p.forms at temperatures >1180 K whereas the passivating orthorhombic GdF forms at lower temperatures. Phase studies56 of EuX2-EuXi systems (X = Cl Br or I) revealed that each pair gives rise to a PbCl,-type structure over a limited composition range. 45 J. Osterwalder H. R. Ott L. Schlapbach J. Schefer and P. Fischer J. Less-Common Met. 1983,94 129. 46 T. Ito B. J. Beaudry K. A. Geschneidner jun. and T. Takeshita Phys. Rev. B:Condens. Matter 1983 27 2830. 47 F. R. Block and H. J. Bahs J. Less-Common Met. 1983 89 77. 48 P. D. Goodell J. Less-Common Met. 1983 89 45. 49 J. J. Sheridan 111 F. G. Eisenberg E. J. Greskovich G. D. Sandrock and E. L. Huston J. Less-Common Met. 1983 89 447. 50 P.S. Rudman G. D. Sandrock P. D. Goodell J. Less-Common Met. 1983 89 437. 5' Jingchun Wang Shuiyu Cai Songyue Yuan and Yue Wu Cuihua Xuebao 1983,4 18. 52 P. D. Goodell and P. S. Rudman J. Less-Common Met. 1983 89 117. 53 D. Noreus L. G. Olsson and P. E. Werner J. Phys. F 1983 13 715. 54 H. Oesterreicher and J. Elton J. Solid State Chem. 1983 48 128. 55 P. C. Nordine R. M. Atkins and A. M.Oener MetalL Trans. A 1983 14 53. 56 S. A. Hodorowicz K. Ewa and H. A. Eick J. Less-Common Met. 1983 93 415. 3 10 S. J. Lyre The EuCl,Br,- (0 s x 2) system has been examined in some detail and three regions identified. From 0 zs x =s0.1 a SrBr,-type structure prevails and for 0.3 x =s2.0 a PbC1,-type structure is found. Between the two types of anion-ordered structure a diphasic region exist^.^' Photoelectron spectra of gaseous halides of Ln fall into two distinct groups depending on whethCr the Ln has a more or lea than half-filled 4f shell.Spectra within each group are very similar to each other. Bonding becomes progressively more covalent in the sequence F < C1 < Br < I for a given Ln.58 The 5D4-+ 'F6 blue fluorescence from TbF3 is properly described by a model which includes fast exciton diffusion across shallow traps. When pumping in the 'D4manifold a U.V. short-lived anti-Stokes fluorescence D3 + F6 is observed ;its characteristics support a description including efficient energy transfer by ~p-conversion.~~ Ce3+ electronic excitation in Gd0.96Ce0.02E~0.0Z F leads to emission only from Eu3+.Direct energy transfer does not occur; Gd3+ acts as intermediary.60 Because of the low site- symmetry of the non-Kramers P8+ in PrF, its ground state is a singlet and PrF3 acts as a Van Vleck paramagnet.61 The products of reaction between Eu and Yb vapour with C12 have been studied in an Ar matrix by i.r. spectroscopy. The products are molecular EuC1 and YbC1 with some evidence for minor amounts of the corresponding LnC1,.62 A more detailed examination of YbC12 in an Ar matrix has provided evidence for the non-linearity of the molecule. On the basis of C1 isotope shifts and relative intensities of v3 and v1 frequencies the bond angle was established6 to be 126 f 5". When heated under vacuum at temperatures >570K reaction 3 occurs producing a non-stoicheiometric C1-deficient compound with the hexagonal UC13-type structure of EuC13 retained down to at least C1 Eu ratios of 2.84 1.Temperature-dependent l5 ' Eu Mossbauer spectra and electrical conductivity data provide evidence for electron exchange between Eu lattice sites in the non-stoicheiometric compound.64 The Dy2'(4flo) valence configuration of Dy in Dy5Cl DyBr, and DyI has been demonstrated by 16'Dy Mossbauer spectroscopy. Unfortunately none of the samples were of high purity and the mixed valence state of Dy in Dy5Clll complicated the interpretation of the temperature-dependent spectra.65 EuCl,(s) -+ EuCl,(s) + ;Cl,(g) (3) Ternary halides containing Ln" or Sc" of formula types Am3 A2RX4 and AR2X5(A = alkali metal X = halogen and R = Sc Sm Eu Dy or Tm) have been reviewed.66 Monochlorides MC1 (M = Sc Y Ln or certain other transition elements) provide a novel metal-like array within tightly bound blocks composed of four cubic-close-packed layers of sequence Cl-M-M-Cl.These compounds 57 S. A. Hodorowicz and H. A. Eick J. Solid State Chem 1983 49 362. 513 B. RuSEiE G. L. Goodman and J. Berkowitz J. Chem. Phys. 1983 78 5443. 59 M. F. Joubert. B. Jacquier R.Moncorge and G. Boulon Stud. Inorg. Chem. 1983 3 558. 60 G. Blasse Phys. Status Solidi A 1983 75 K41. 61 L. Nielson J. Less-Common Met. 1983 94,243. 62 N. S. Loktyushina S. B. Osin and A. A. Mal'tsev Zh. Neorg. Khim. 1983 28 2436. " I. R. Beattie J. S. Ogden and R. S. Wyatt J. Chem. SOC.,Dalton Trans.1983 2343. 64 J. Ball C. M. Jenden S. J. Lyle and W. A. Westall J. Less-Common Met. 1983 95 161. 65 J. M. Friedt J. MacCordick and J. P. Sanchez Inorg. Chem. 1983,22,2910. 66 G. Meyer J. Less-Common Met. 1983 93 371. Sc Y the Lanthanides and the Actinides 311 appear to be metallic67 and can be involved in compound formation by interstitial insertion of small non-metal atoms within the tetrahedral or trigonal-antiprismatic interstices between the M layers as well as simultaneous or separate intercalation of alkali metal cations in the van der Waals gap between Cl layers. New phases such as Lio.09YC1 and YC1Co,5 are produced by stoicheiometric reaction. An interest-ing compound Gd12C6II7 has been prepared by heating Gd + GdI + graphite in a Ta capsule.Black shining monoclinic crystals were obtained and found to consist of linear units of three condensed Gd6II2 clusters linked through cis edges. The centres of the Gd6 octahedra are occupied by C2 units.68 In the system NaF-YbF, eutectics occur at 598 and 915 "C at which YbF is 28 and 75 mol.% re~pectively.~~ Inthe MBr-TbBr systems (M = Na or K) compounds of composition 3MBr.2TbBr3 and 3MBr.TbBr3 are formed.70 Dehydration of LaC13.7H20 to LaCl has been re-examined and two new inter- mediates LaC13.5H20 and LaC13-2H20 identified.71 A study of the thermal decomposition of EuX3.6H20 (X = Cl or Br) has shown by '"Eu Mossbauer spectroscopy that at least part of the Eu"' in X = Br but not X = C1 undergoes a valence change to Eu" in the course of water removal which occurs by dehydration and hydrolytic processes.The bromide is intermediate between the corresponding chloride and iodide systems since in the last mentioned a complete or near complete change to Eu" occurs.72 An examination of vapour phase hydrolysis of SmBr to SmOBr from 699-860 K enabled the thermodynamic quantities AHo = 61.05 and AGO = 27.20 for the reaction and AH:(SmOBr) = -965.3 kJ mol-' to be calcu- lated.73 The structure of [Ed& (OH2)6]C1 has been redetermir~ed~~ and structural refinement of LaOCl agrees with previous powder Most of the work on binary chalcogenides LnX (X = S Se or Te) relates to potentially mixed-valence systems which behave as magnetic semi-conductors. This work extends to ternary mixed lanthanide systems with a common X mixed X systems with a common Ln and to LnX diluted magnetically by substitution of some Ln by a diamagnetic metal ion e.g.Sr2'. Vapour phase growth of EuX (X = S,Se or Te) has been studied at 1963-2323 K using electron-beam induced reactions between the elements. Crystal growth reflects a diffusion mechanism involving dissociative sublimation. The products have the expected electrical properties and lattice parameter^.'^ Films of EuS with good crystal form have been grown by molecular beam epitaxy on silica substrates and some sandwich and mixed films described.77 The black semiconductor phase of SmS changes to the golden phase under pressure. According to a recent theoretical model the latter is a narrow gap semiconductor with a valence band consisting of states 67 J.E. Ford J. D. Corbett and Shiou-Jyh Hwu Znorg. Chem. 1983 22 2789. A. Simon and E. Warkentin 2. Anorg. Allg. Chem. 1983 497 79. 69 P. P. Federov A. V. Rappo F. M. Speridonov and B. P. Sobolev Zh. Neorg. Khim. 1983 28 744. 7o A. G. Dudareva A. B. Strekachinskii G. Tamerat 0. V. Polyanskaya and A. I. Ezhov Zh. Neorg. Khim. 1983 28 1073. Zheng Gong Peiheng Chen Zhizhen Guo Jinhua Ma and Yunsheng Chen Xuaxue Xuebao 1983 41 391 (Chem. Abstr. 1983 99 186366). 72 S. J. Lyle and W. A. Westall Thermochim Acra 1983 68 51. 73 V. Wishnevsky F. Weigel M. Eiswirth and R. Schwankner J. Less-Common Met. 1983 91 309. 74 D. L. Kepert J. M. Patrick and A. H. White Ausr. J. Chem. 1983,36,477. 75 L.H. Brixner and E. P. Moore Acta Cryst.;Sect. C Cryst. Srruct. Commun. 1983 39 1316. 76 S. I. Vel'mizov V. K. Gartman L. A. Klinkova Izu. Akad Nauk SSSR Neorg. Muter. 1983 19 31. 77 W. Zinn B. Saftic N. Rasula M. Mirabal and J. Koehne J Magn. Magn. Muter. 1983 35 329. 312 S. J. Lyle with mixed ~alence.~' Measurements at 220-410 K showed that piezoresistivity is isotropic in SmSe." In the EuX series magnetic properties comprise ferromagnetism (EuO EuS) metamagnetism (EuSe) and antiferromagnetism (EuTe). Faraday rotation and magnetization with the former almost proportional to the latter has been observed for EuS and EuSe in megagauss fields." Raman scattering in EuTe at low temperatures has been studied and the dependence of line shapes on excitation energy interpreted in terms of modulation of 5d spin-orbit interaction by lattice displacement.81 A high pressure high magnetic field '"Eu Mossbauer spectroscopic study on pure EuX (X = S Se or Te) and magnetically diluted Eu,Sr,-,S systems confirms expected relations between magnetic exchange interactions and transferred hyperfine (t.h.f.) fields.The pressure dependence of the total h.f. field in the ferromagnetically saturated state of EuX is mainly due to the pressure response of the t.h.f. field of nearest Eu neighbours. EuO excepted the t.h.f. fields of next nearest Eu and the Eu-core polarization field are almost insensitive to pressure.'2 The 153E~ n.m.r. in single crystals of EuSe was observed by a pulse technique in fields S6.6 T below 4.2 K.The frequency in the ferromagnetic state was fitted within the framework of a spin-wave theory using an artificial internal field and J, J2 exchange para- meter~.'~ Specific heat capacity measurements on antiferromagnetic TmS TN = 5.17 K have shown that above TN,in addition to the classical yT + pT3 terms there is an extra contribution which can be fitted to a triplet ground-state Schottky- like an~rnaly.'~ A modulated antiferromagnetic structure has been detected in TmS below TN .85 The critical composition for observations on the transitions from the black semi- conducting to the gold metallic state in Sm -x Gd S is at x = 0. 16.'6,87Measurements of lattice parameter as a function of temperature (12-300 K) for the x = 0.18 compound showed that the limits of the temperature region in which the two phases co-exist depends on the direction but not the number of cycles through the transition.The EXAFS data for the first nearest neighbour S atoms of each Sm can be fitted to a mean distance and a [Sm2+]/[Sm3+] ratio which corresponds to the valence deduced from LIIIedge X-ray absorption meas~rernents.'~ M-edge X-ray absorption spectra have been advocated as a new tool for the determination of valence in mixed-valence systems. For Tm compounds such as Tm,Y,-,Se the spectra are superpositions of Tm3+ (3 lines) and Tm2+ (1 line) components." Crystallographic investigations in Eu -x Sm Se have shown that the lattice-constant dependence on x deviates from the Vegard law prediction consistent with an intermediate valence 78 K.A. Kikoin Zh. Eksp. Teor. Fiz. 1983,855 1000. 79 S. I. Grebinskii V. V. Kaminskii N. N. Stepanov I. A. Smirnov and A. V. Golubkov Fiz. Tverd. Tela (Leningrad) 1983 25 151. 80 M. Suekane G. Kido N. Miura and S. Chikazumi J. Magn. Magn. Mater. 1983,31-34 589. " Y. Ousaka 0.Sakai and M. Tachiki J. Phys. SOC.Jpn. 1983 52 1034. 82 Ch. Saur A. M. Zaker and W. Zinn J. Magn. Magn. Mater. 1983 38,225. 83 M. Kawakami H. Luetgemeier H. G. Bohn and K. Fischer J. Magn. Magn. Mater. 1983,31-34,425. 84 J. Peyrard J. Flouquet P. Haen F. Lapierre Y. Lassailly F. Holzberg and C. Vettier J. Magn. Magn. Mater. 1983 31-34 433. Y. Lassailly C. Vettier F. Holtzberg J. Flouquet C. M. E. Zeyen and F. Lapierre Phys. Rev. B Condens.Matter 1983 28 2880. 86 V. V. Kaminskii A. A. Vinogradov N. N. Stepanov and I. A. Smirnov Pis'ma Zh. Tekh. Fiz. 1983,9 624 (Chem. Abstr. 1983,99 46264). 87 C. Godart J. C. Achard G. Krill and M. F. Ravet-Krill J. Less-Common Met. 1983 94 177. 88 G. Kaindl W. D. Brewer G. Kalkowski and F. Holtzberg Phys. Rev. Lett. 1983 51 2056. Sc Y the Lanthanides and the Actinides 313 of about 2.3 at x S 0.2 for Sm in the EuSe host. The non-magnetic Sm with smaller ionic radius than Eu2+influences the magnetic properties of the A semicon-ductor to metal transition occurs for x =r 0.2 in Yb,-,Tm,S films with a Tm valency change. For x s 0.18 lattice constant optical absorption and resistivity data support the absence of a pure Tm3+ ground state.g0 The properties of TmSe and related ternary systems with part substitution of Tm by another Ln or Se by another chalcogen have been summarized?' Mixed valence EU304 is produced by exposure of evaporated Eu film to 02.92 From an analysis of core-level satellites in the photoemission spectrum it was concluded that Ce02 formerly thought to be tetravalent is a mixed valence com- pound with 4fo.46.The magnetic moment of the 4f configuration is quenched through singlet coupling between the 4f electron and the oxygen 2p hole.93 The superconduct- ing properties of La2X3 and La3X4(X = S or Se) have been re~iewed.9~ The a.c.resistivity of single crystals of Sm3S4 was measured at frequencies ZG 1.5 GHz. Tunnelling conduction by 4f electrons of Sm2+ was observed at low temperatures.'' Examination of the non-stoicheiometric Yb3S4 phase in the range YbSl,34 to YbSl,4* by electron diffraction has led to the conclusion that this is not as reported earlier a homogeneous solid-solution region with the Yb S4 structure; longer range structure modulation is evident.96 Two orthorhombic modifications of LaYbS3 are known in which both the La and Yb are in planar or near planar layers which alternate with S.The co-ordination of La decreases from the lower to the higher temperature form but Yb remains in octahedral ~o-ordination.~~ Treatment98 of simple lanthanide salts by alkali metal thiocyanate melts produces Ln4S7 (Ln = La Pr or Nd) and not Ln2S3 as previously reported. LnMo6Ss and related Chevrel phases are of interest as superconductors.Recent neutron-scattering investigations which have attempted to elucidate the nature of the modulated phase in HOMOS are reviewed.99 Mossbauer isomer shifts have shown"' that Yb is divalent in YbMo6S8. Replacement of Yb by La in YbMo6Sg and YbMo6Seg throws light on the effect of replacing a two-electron by a three- electron donor on crystal parameters and superconducting critical temperatures T,. Replacement results in a marked increase in T in Yb1-,La,Mo6Ses whereas in the sulphide T changes relatively little from x = 0 to 1 .O. The effect of unit-cell volume and electron donation on the shape of the density-of-states curve are discussed and it is concluded that a rigid band model is unable to explain the observations.'" In 89 K.Kojirna S. Nishizawa K. Hiraoka T. Hihara and T. Kamigaichi Solid State Commun. 1983,46,417. D. Jeanniot G. Brun and G. Zribi Phys. Rev. B Condens. Matter 1983 27 6166. 91 P. Wachter J. Magn. Magn. Muter. 1983 31-34 439. 92 J. Barth F. Gerken J. Schmidt-May A. Flodstroem and L. I. Johansson Chem. Phys. Lett. 1983 96 532. 93 A. Fujirnori Phys. Rev. B Condens. Matter 1983 28 4489. 94 A. M. Gabovich and D. P. Moiseev Visn.Akad. Nauk Ukr. RSR 1983,22(Chem.Abstr. 1983,98,225798). 95 A. Tamaki T. Goto M. Sugita S. Kunii T. Suzuki T. Fujimura and T. Kasuya J. Magn. Magn. Muter. 1983 31-34 383. 96 C. Otero Diaz and B. G. Hyde Acta Cryst. Secr. B Stmct. Sci. 1983 39 569. 97 N. Rodier R. Julien Vovan Tien Acta Cryst. Sect. C Cryst. Struet.Commun. 1983 C39 670. 98 G. F. Balashevskii and V. K. Val'tsev Zh. Neorg. Khim. 1983 28 1677. 99 R. Pynn J. W. Lynn and J. Joffrin Helv. Phys. Acta 1983 56 179. I00 J. D. Jorgensen D. G. Hinks D. R. Noakes P. J. Viccaro and G. K. Shenoy Phys. Rev. B Condens. Matter 1983 27 1465. 101 J.-M. Tarascon D. C. Johnson and M. J. Sienko Inorg. Chem. 1983 22 3769. 314 S. J. Lyle MMO,(S1-,sex)8 with M = La Sm Eu Yb Pb or Ag and 0 < x < 1 the hexagonal c/a ratio has a minimum when plotted against x. The apparent cause of the minimum deepest for La and shallowest for Ag is a strong preference by Se for occupancy of the general position chalcogen site rather than the special position site on the 3 axis. The preferred site ordering is greatest for M3+ least for M+ with M2+ intermediate.lo2 LaPd3S4 which may be formulated as [LaPd3S4 + el has the NaPt304-type structure. From its electrical conductivity it is claimed to be the first metallic Pd bronze to be re pa red.''^ Eu2SnS5 and Sr,SnS are isostructural with the Eu being bi~a1ent.l'~ has an interesting structure in which La is inside a bicapped triangular prism of Te with the polyhedra connected so that they create pentagonal tunnels in the (001) direction; the Cu are in positional disorder in the tunnel^.''^ All metallic sites are fully occupied in La,Mn,Ga,S14 with each La in a distorted bicapped trigonal prism.Io6 Binary and ternary pnictides are of some interest because of their magnetic and mixed valence properties. From a mass spectrometric study of the dissociation of EuP from 100 to 1400 K the heat of atomization at 298 K was found'" to be 797.9 f 12.6 kJ mol-'.The magnetic properties of Ce monopnictides have been reviewed.lo8 Mossbauer spectroscopy has shown that Eu4As3 contains both Eu" and Eu"' and there is evidence for temperature-induced valency fluctuations as in Eu3S4.109 Contrary to expectations based on the behaviour of CeP a pressure- induced valence change in CeAs at s32 GPa is not evident."' '"Eu Mossbauer studies on EuX2P2(X = Fe Co or Ni) indicate that Eu is bivalent and magnetically ordered at low temperatures in the compounds with X = Co and Fe but of intermedi- ate valence in X = Ni."' In EuFe4P12 the ferromagnetic ordering temperature (100 K) is very high in view of the large Eu-Eu distances (6.8 A).'' Ternary silicide systems represent an interesting but complex group of substances for study on account of their superconducting properties.One of the systems of main interest centres on CeCu2Si2-T has been determined for the alloy systems (Ce M)Cu2Si2 (M = La Y or Sc) Ce(Cu T),Si2 (T = Ag Au Mn Ru Rh or Pd) and CeCu,(Si,Ge) in addition to CeCu2Si2 samples of variable stoicheiometry.' 1311 l4 The highest T values are obtained from Cu-rich CeCu2Si2.' l4 From a study of the new silicides LaRh3Si (l) LaRh2Si2 (2) LaRhSi (3) La2Rh3Si (4) LaRhSi (5) and La2RhSi3 (6) it was found that all but (I) and (6) are I02 D. C. Johnson J.-M. Tarascon and M. J. Sienko Znorg. Chem. 1983 22 3773. 103 D. A. Keszler and J.A. Ibers Znorg. Chem. 1983 22 3366. 104 M. Guittard S. Jaulmes M. Julien-Pouzol E. Barthelemy and J. Flahaut C.R. Seances Acad. Sci. Ser. 2 1983 296 249. I05 Huy Dung Nguyen M. P. Pardo and P. Boy,Acta Cryst. Sect. C Cryst. Stmct. Commun. 1983,39,668. I06 N. Rodier M. Guittard and J. Flahaut C.R. Seances Acud. Sci.. Ser. 2 1983 2% 65. 107 S. P. Gordienko and K. E. Mironov Izv. Akad. Nauk SSSR Neorg. Mater. 1983 19 151. I08 J. Rossat-Mignod P. Burlet S. Quezel J. M. Effantin D. Delacote. H. Bartholin 0. Vogt and D. Ravot J. Magn. Magn. Mater. 1983 31-34 398. Io9 R. Nagarajan E. V. Sampathkumaran and R. Vijayaraghavan Phys. Status Solidi A 1983 75 K149. 110 A. Werner H. D. Hochheimer R. L. Meng and E. Bucher Phys. Lett. A 1983,97 207.Ill R. Nagarajan E. V. Sampathkumaran L. C. Gupta R. Vijayaraghavan and G. K. Shenoy f. Magn. Magn. Muter. 1983 31-34 757. 112 A. Gerard F. Grandjean J. A. Hodges D. J. Braun and W. Jeitschko J. Phys. C 1983 16 2797. 1 I3 H. Spille U. Rauchschwalbe and F. Steglich Helv. Phys. Acta 1983 56 165. 114 M. Ishikawa H. F. Braun J. L. Jorda Phys. Rev. B Condens. Matter 1983 27 3092. Sc Y the Lanthanides and the Actinides 315 superconductors above 1.6 K. A correlation was noted between T and valence electron concentration per atom for which a value between 4.5 and 6.3 was required for superconductivity.' l5 LaIr2Si2 has high- and low-temperature forms with the CaBe2Ge2- and the ThCr2Si2-type structures respectively. The former can be quenched from above the transition temperature (1720 "C)and becomes supercon- ducting at 1.6 K whereas the latter is normal down to 1 K.'16 Y2M03Si4 is a superconductor.'l7 Both LaMn2 Si2 and YMn2Si2 crystallize in the ThCr2Si2-type tetragonal system and form a complete solid-solution range without structural change.In La,-,Y,Mn2Si2 ferromagnetic ordering occurs for x < 0.2 and antifer- romagnetic ordering for x > 0.2 with Mn-Mn distances the determining factor."* Magnetic and neutron-diffraction studies in TbNi2Si2 HoCo2Si2 and TbCo2Si2 revealed a collinear antiferromagnetic ordering below 10 13 and 30 K respectively with Ln moments orientated along the c axis."' CeOs2Si2 is isotypic with ThCr2Si2.'20 Compounds in which Er is replaced by Dy Ho or Tm are isotypic to Er2Pd2Si crystallizing in the orthorhombic system.I2' Ce'" oxidizes water to O2 in the presence of Ru02 catalyst in 0.5 M H2S04.122 Formate complexed by Ed" in HC02 H-Na02CH buffer decomposes on irradiation at 254 nm to H+ and C02-by processes involving charge transfer to Eu"'.'~~ The one-electron reduction kinetics of the cryptates Eu(2.2.1)3+ and E~(2.2.2)~+ by V" and Eu" in aqueous solution has been studied polarographically to examine the effects of encapsulating Eu within the ligand cavities on the Eu(III)/(II) couple. The rate constant for Eu(III)/(II) self-exchange increases by lo7 and 2 x lo4 on incorporation of Eu in (2.2.1) and (2.2.2) cryptates respectively a result taken to imply that nonadiabaticity is not primarily responsible for the low reactivity of aquated Eu~'"~~.' 24 Complex formation between anion and cation in concentrated solutions of Ce(NO,) is confirmed by Raman spectro~copy'~~ and excitation spec- troscopy of the 'F + 5D0transition in Eu"' provides a direct measure of inner complexation of Eu"' by SCN- C1- and NO3- in aqueous solutions.'26 A study of pH dependence of the circularly polarized luminescence spectra obtained from Tb"' and Eu"' complexes with chiral aminopolycarboxalate (APC) ligands revealed sharp configurational changes between pH 10.5 and 1l.'27 Increase in luminescence intensity from certain Tb(APC) complexes at high pH was concluded to be due to p-hydroxy-bridged polymeric species.'2s 'H N.m.r.spectra of ethylenediamine- tetrakis( methylenephosphoric acid) and some LnIrr complexes in solution were I15 B.Chevalier P. Lejay M. Vlasse J. Etourneau and P. Hagenmuller Stud. Inorg. Chem. 1983 3 683. 1I6 H. F. Braun N. Engel and E. Parthe Phys. Rev. E Condens. Mutter 1983,28 1389. 1 I7 F. G. Aliev Yu. K. Gorelenko V. V. Moshehalkov and R. V. Skolozdra Fiz. Nizk. Temp. (Kieu) 1983 9 197 (Chem. Abstr. 1983 99 97574). 1 I8 E. V. Sampathkumaran R. S. Chaughule K. V. Gopalakrishnan S. K. Malik and R. Vijayaraghavan J. Less-Common Met. 1983 92 35. 1IY V. N. Nguyen F. Tcheou J. Rossat-Mignod and R. Ballestracci Solid State Commun. 1983 45 209. I20 C. Horvath and P. Rogl Muter. Res. Bull. 1983 18 443. I21 K. Klepp E. Hovestreydt and E. Parthe Actn Cryst. Sect. C Cryst. Stmct. Commun.1983 39 662. I22 J. Kiwi M. Gratzel and G. Blondeel J. Chem. Soc. Dalton Trans. 1983 2215. 123 N. Ammo A. Matsurnoto and J. Shiokawa Polyhedron 1983 2 63. I24 E. L. Yee J. T. Hupp and M. J. Weaver Inorg. Chem. 1983 22 3465. 125 R. Carniniti P. Cucca and A. D'Andrea Z. Nuturforsch. A Phys. Phys. Chem. Kosmophys. 1983,38 533 126 P. J. Breen and W. D. Horrocks jun. Znorg. Chem. 1983 22 536. 127 H. G. Brittain and K. H. Pearson Inorg. Chem. 1983 22 78. 12' L. Spalding and H. G. Britain Inorg. Chem.. 1983 22 3486. 316 S. J. Lyre interpreted to indicate that the N-atoms are preferentially protonated in the free ligand whereas the free phosphonate groups protonate in the Ln complexes. Spectra are consistent with a time-averaged symmetry for the ligand about the Ln involving long-lived Ln-N and short-lived Ln-0 bonds.129 A new method involving emission-intensity-time measurements following laser excitation of a selected Eu"' species has been advocated for the study of equilibrium dynamics involving complex f~rmation.'~' The complexes Dy(CA):- and Tm(CA)$- derived from 4-hydroxy- pyridine-2,6-dicarboxylic acid (H3 CA) have been tested as aqueous shift reagents for metal cations.Significant shifts are produced by an interaction which is labile on the n.m.r. time scale between cation and shift reagent anion.131 Ce02 and simple Ce'" salts dissolve in HSO3C1 to form Ce(SO3C1) which behaves as a non-electrolyte but Th'" and La''' give H2Th(S03C1)6 and HLa(S03Cl) both of which behave as weak acids in HSO3C1 as solvent.'32 Bis(4,5-dimethyl- N,N,N' N'- tetrapropyl-3,6-dioxo-octane diamide) europium( 111) tetrafluoroborate was prepared by reacting Eu metal with NOBF in MeCN followed by treatment with 2 mol of compound (7).From laser excitation and emission spectra the structure is consistent with that known for an analagous Ca" complex. The Eu"' site symmetry The 1 1 inclusive complexes of the bifunctional cryptand (8) is D~~or 10wer.l~~ (7) with La3+ P3+,and Eu3+ have been prepared and ~haracterized.'~~ The 1 1 complexes of Ln"' with diazapolyoxamacrocycles [2.1] and [2.2.1] in anhydrous MeOH or propylene carbonate are more stable than those with macrocyclic poly- ethers; the bicyclic [2.2.1] cryptates are more stable than the monocyclic [2.1] complexes.135 The stability constants of complexes formed by the cryptands [2.2.2] and [2.2.1] and [2.1.1] with Ln3+(Ln = Pr Nd Gd Ho or Yb) and Ca2+ S8+ and Ba2+ were measured in DMSO."* Metal-ion specificity similar to that in water is observed for alkaline earth ions but not for Ln3+.Tris[hydridotris(pyrazol-1-yl)borato]ytterbium(~~~) in CH2C12 is a rare example of a solution-rigid Ln com- ~1ex.I~~ For Ln(ClO,) in DMF equilibria of the kind shown in equation 4 are I29 E. N. Rizkalla and G. R. Choppin Inorg. Chem. 1983 22 1478. 130 W. D. Horrocks jun. V. K. Arkle F. J. Liotta and D. R. Sudnick J. Am. Chem. SOC.,1983 105 3455. 131 M. M. Pike D. M. Yarrnush J. A. Balschi R. E. Lenkinski and C. S. Springerjun. Inorg. Chem.1983 22 2388. I32 J. Puri P. Singh and J. M. Miller Inorg. Chim. Acta 1983 74 139. 133 M. Albin A. C. Goldstone A. S. Withers and W. D. Horrocksjun. Inorg. Chem. 1983 22 3182. 134 0.A. Gansow and R. A. Kausar Inorg. Chim. Acta 1983 72 39. 135 M. C. Almasio F. Arnaud-Neu and M. J. Schwing-Weill Helv. Chim. Acta 1983 66,1296. I36 R. Pizer and R. Selzer Inorg. Chem. 1983 22 1359. 137 M. V. R. Stainer and J. Takats J. Am. Chem. SOC.,1983 105 410. Sc Y the Lanthanides and the Actinides 317 evident for Ln = Ce to Nd but the only stable species Ln(DMF)i+ + DMF e Ln(DMF):+ (4) from Ln = Tb to Lu is Ln(DMF);+.l3' In a CPL spectroscopic study of tris (D,D-dicampholyl methanato)europium( 111) in 40 different solvents strong optical activity could be observed within the 5D,+7F,and 5D0+7F2transitions in Eu"' in many of them.'39 Chiral complexes of the Ln have been re~iewed.'~' Reaction of an anhydrous Ln"' halide with a secondary amine and C02 produced the first N,N-dialkylcarbamato complexes Ln (02CNR2)3,.'41 The 15-crown-5 ether complexes of Ln(N03) and Nd( NO3) give crystals of composition Ln( NO3)3.L with the Ln inserted in the space between three NOS ions and the crown.142 Crystals of Sm(N03),.L-H20 where L is 2-methoxy-l,3-xylyl)- 18-crown-5 have each Nd co-ordinated to three 0-atoms from L six from 3NOT and one from H20.14 By contrast Nd(C104),.L.5H20 where L is 15-crown-5 has Sm nine-co-ordinated to oxygen five from L and four from H20.Ia The inability of Ln3+ to penetrate the 'cavity' of the crown ethers helps to account for lack of ~pecificity'~~ noted above.Only a few preparative and structural studies involving organometallic compounds have been published. An X-ray structural analysis'45 of sublimed tricyclopentadienyl praesodymium( 111) confirms the presence of a singular polymeric chain in the solid involving q5-co-ordination of each Pr with three neighbouring Cp ligands and q2-co-ordination with a fourth bridging Cp ligand ;this structure differs markedly from that reported in 1969. By treating Cp,YCl with AlH,.NEt in benzene crystals of {Cp,YCl.AlH,.NEt,} were obtained. This compound is a Cp2YCl dimer bonded to AlH,.NEt by H bridges between Y and A1 as well as by a weak Al-C1 bond. The C1 Y Al and H atoms are coplanar.'46 Whereas the diphosphine Me2PCH2CH2PMe2 reacts with Ln( Me5C5),( OEt) to give hydrdcarbon-insoluble Ln(Me5C5)2(Me2PCH2CH2PMe2) where Ln = Eu or Yb the ligand Me,PCH,PMe gives soluble LII(M~~C~)~M~,PCH,PM~,.In toluene the Yb compound reacts with YbCl to give Yb(MeSC5),C1(Me2PCH2PMe2) in which the Yb is co-ordinated to the 2MeSC5 groups C1 and one P atom of MezPCH2PMe2.'47 4 The Actinides This year has seen the publication of a book dealing with the physical properties of An corn pound^,^^' a volume in the A.C.S. Symposium Series on the chemistry 138 D. L. Pisaniello L. Helm P. Meier and A. E. Merbach J. Am. Chem. Soc. 1983 105,4528. 139 H. G. Brittain J. Chem. SOC,Dalton Trans. 1983 1 165. I40 H. G. Brittain Coord. Chem. Rev. 1983 48 243.141 D. B. Dell'Amico F. Calderazzo F. Marchetti and G. Perego J. Chem. SOC.,Dalton Trans. 1983,483. I42 Pinzhe Lu Cheng Shen Yuguo Fan Sougchun Jin Shugong Zhang and Fengian Yu Fenzi Kexue Yu Huaxue Yanjiu 1983 3 77 (Chem. Abstr. 1983 99,46322). '43 G. Tomat G. Valle A. Cassol and P. Di Bernado Inorg. Chim. Acta 1983 76 L13. 144 T. J. Lee Hrong Roang Sheu T. L. Chiu C. T. Chang Acta Cryst. Sect. C Cryst. Struct. Commun. 1983 C39 1357. 145 W. Hinrichs D. Melzer M. Rehwoldt W. Jahn and R. D. Fischer J. Organomet. Chem. 1983,251,299. 146 E. B. Lobkovskii G. L. Soloveichik B. M. Bulychev A. B. Erofeev A. I. Gusev and N. I. Kinllova J. Organomet. Chem. 1983 254 167. I47 T. D. Tilley R. A. Andersen and A. Zalkin Znorg. Chem 1983 22 856. I48 P.Erdos and J. M. Robinson 'The Physics of Actinide Compounds' Plenum Press New York 1983. 318 S. J. Lyle of and a short work on the electronic structure and properties of uranyl compounds in Russian. 50 Several useful reviews have appeared including such topics as the role of 5f electrons in transthorium chemistry,"' chemistry of the elements Es and beyond,'52 and the properties of systems involving lower oxidation states of the An.'53 In the last-mentioned review similarities between bivalent An and alkaline earth ions are emphasized. A plot of effective magnetic moment for compounds containing An with 4f0to 4f'O configurations indicate that simple L-S coupling generally accounts for the observed moments ; differences between An and Ln are influenced by the spatial delocalization of the 5f electrons compared with their 4f counterpart^.'^^ Mossbauer spectroscopy with An elements155 and in An research'56 has also been reviewed.The recovery of gram quantities of 230Thand 231Pa by liquid-liquid extraction procedures has been re~0rted.l~~ Pa metal in gram quantities has been prepared by a modified van Arkel process.'58 The a-to &phase transition was found to be at 1042 K in Am'59 and Cf metal transforms sluggishly under pressure from a double hcp to afcc structure.'60 p-UF5 can be prepared in multigram quantity by controlled low-temperature reduction of UF6 with PF3 inUUCUO.~~~ UF6 + Me3SiX (X = C1 or Br) in 1 1 mole ratio in halogenocarbon solutions yield &UF5 at room temperature; with 2 mole equivalents of Me Sic1 the product is UF4.162 Self-consistent thermodynamic data have been tabulated for UF4(s and g) U4F17(s) U2F9(s) UF5(s and g) UZFIO(g) and UF,(s 1 and g).'63*'64 Neutron-diff raction studies on UF confirm that the orthorhombic phase persists down to 77 K.165A new interpretation based on the 19 F n.m.r.spectrum of UF in a magnetic field of 5T,is proposed for the n.m.r. spectra of hexafluorides in solids. The model explains the contradiction with the earlier interpretation and corrects the conclusion regarding the symmetry of UF,.', Strong evidence comes from electron spectroscopic measurements in the gas phase that the highest occupied molecular orbital in UF is of t, and not tl ~yrnmetry.'~' Quantum yields of near unity were obtained in the photodissociation of hF6 mixtures in NZ,Xe or Arbut not in F2 using laser radiation at 337nm.I6* The I49 'Plutonium Chemistry' A.C.S.Symposium Series vol. 216 ed. W. T. Carnal1 and G. R. Choppin A.C.S. Washington D.C. 1983. I5O V. A. Glebov Elektronnoe Stroenie i Svoistva Uranil'nykh Soedinenii Energoatomizdat Moscow 1983 (Chem. Abstr. 1983 99 200953). C. K. Jorgensen Radiochim. Acta 1983 32 1. E. K. Hulet Radiochim. Acta 1983 32 7. 153 N. B. Mikheev Radiochim. Acta 1983 32 69. I54 P. G. Huray S. E. Nave and R. G. Haire J. Less-Common Met. 1983 93 293. W. Potzel J. Moser L. Asch and G. M. Kalvius Hyperfne Interact 1983 13 175. J. M. Friedt Radiochim. Acta 1983 32 105. 157 M. R. Hertz P. E. Figgins and W.R. Deal Report MLM-2985 1983 (Chem. Abstr. 1983,99,45049). I58 J. C. Spirlet E. Bednarczyk and W. Mueller J. Less-Common Met. 1983 92 L27. I59 V. D. Shushakov A. G. Seleznev N. S. Kosulin and T. V. Shushakova Fiz. Met. Metalloved 1983 55 405. J. R. Peterson U. Benedict C. Dufour I. Birkel and R.G. Haire J. Less-Common Met. 1983,93 353. 16' T. A. O'Donnell R. Rietz and S. Yeh J. Fluorine Chem. 1983 23 97. 162 D. Brown J. A. Berry J. H. Holloway and G. M. Staunton J. Less-Common Mer. 1983 92 149. I63 J. M. Leitnaker Report K/PS-352 1983 (Chem. Abtr. 1983,99 147096). 164 J. M. Leitnaker High Temp. Sci. 1983 16 239. J. H. Levy J. C. Taylor and A. B. Waugh J. Fluorine Chem. 1983 23 29. 166 E. P. Zeer 0. V. Falaleev and V. E. Zobov Chem. Phys.Lett. 1983 100 24. 167 N. Maartensson P. A. Malmquist and S. Svensson Chem. Phys. Lett. 1983 100 375. I68 K.C. Kim and G. Campbell Chem. Phys. Lett 1983 98 491. Sc Y the Lanthanides and the Actinides 319 chemistry of ThBr has been reas~essed.'~~ Polarized absorption and emission spectra of Pa4' in ThBr and ThC14 host lattices have been obtained from 4.2 to 300 K in the i.r. spectral range. The seven crystal field levels of the 5f' configuration were determined and fitted by a model assuming D2dsite ~yrnrnetry.'~' From i.r. spectra for UX4 taken in a He atmosphere asymmetric valency vibrations (single bands) were observed at 550 345 and 233 cm-' for X = F C1 and Br re~pectively.'~' An elegant preparation of Th12has been described'72 and two crystalline forms of Am13 have been identified.'73 Evidence has been obtained from electron microscopy for the presence of chains of oxygen defect clusters in hyperstoicheiometric UOz as previously predicted from a co-ordination model based on chained clusters parallel to the (1 10) dire~ti0n.I~~ The effects of accommodation of such oxygen clusters on the crystal structure have also been considered.' 75 Thermochemical regularities among the oxides of Ln and An have been re~iewed."~ Specific heat measurements in U02 indicate a sharp first-order transition at 30.3 K rather than the A-type anomaly previously reported at 28.7K as a consequence of magnetic ordering.'77 However neither magnetic ordering nor lattice distortions were found at the phase transition in NpOz at 25 K.'78 Cm203 exhibits Curie-Weiss behaviour from 100 to 300 K ordering antiferromag- netically at 13 f 2 K.'79 Pu202Xcompounds (X = 0,S or Se) are all antiferromag- netic.'" Single crystals of Nd2USe and Ndo,5Uo,5Se2 produced by gas transport are ferromagnetic ordering at 24 and 34 K respectively.'" XPS measurements suggest that both U and Sb are five-valent in USb3OIo and USb05.'82 U has pentagonal bipyramidal co-ordination in UMo208which consists of layers of oxide- bridged U and Mo connected by infinite interlayer M-0-M (M = U or Mo) chains.lS3 In a first observation of its kind for f electrons a 5f-like photoemission peak appears at EF= -0.78 eV in normal emission from UN along the (100) plane on cooling below TN= 53 K.The corresponding antimonide with localized 5f electrons does not exhibit such a temperature effect.'' Spin-orbit coupling induces a pre- dominant orbital magnetic moment (-1.5 p B) antiparallel to the spin moment (1.0 pB) in the spin polarized energy bands of UN; the pressure dependence of the I69 R.Guillaumont Radiochim. Acta 1983 32 129. 170 J. C. Krupa S. Hubert M. Foyentin E. Gamp and N. Edelstein J. Chem. Phys. 1983 78 2175. I71 V. M. Korva and I. V. Shikh Zh. Struct. Khim. 1983 24 172. 172 N. Kumar and D. G. Tuck Inorg. Chem. 1983 22 1951. 173 R. G. Haire J. P. Young and J. R. Peterson J. Less-Common Met. 1983 93 339. I74 G. C. Allen J. T. Buswell and P. A. Tempest J. Chem. Soc. Dalton Trans. 1983 589. 175 G. C. Allen and P.A.Tempest J. Chem. Soc. Dalton Trans. 1983 2613. 176 L. R. Morss J. Less-Common Met. 1983 93 301. I77 G. D. Khattak Phys. Status Sofidi A 1983 75 317. 178 A. Boeuf R. Caciuffo J. M. Fournier L. Manes J. Rebizant F. Rustichelli J. C. Spirlet and A. Wright Phys. Status Solidi A 1983 79 K1. I79 L. R. Morss J. Fuger J. Goffart and R. G. Haire Inorg. Chem. 1983 22 1993. 180 J. M. Costantini D. Damien C. H. De Novion A. Blake A. Cousson H. Abazli and M. Pages J. Solid State Chem. 1983 47. 210. 181 V. K. Slovyanskikh N. T. Kuznetsov N. V. Gracheva V. I. Chechernikov and P. V. Nutsubidze Zh. Neorg. Khim. 1983 28 1388. 182 R. Dolobel H. Baussart J. M. Leroy J. Gimblot and L. Gengembre J. Chem. SOC., Faraday Trans. I 1983 79 879.I83 T. L. Cremers P. G. Eller R. A. Penneman and C. C. Herrick Acta Cryst. Sect. C Cryst. Struct. Comrnun. 1983 C39 1163. I84 B. Reihl G. Hoilinger and F. J. Himpsel Phys. Rev. B Condens. Matter 1983 28 1490. 320 S. J. Lyle moment and the large magnetic anisotropy then become compatible with itinerant- electron theory.'s5 Reflectivity measurements on the ferromagnets U3 P4 and U3As4 and the isostructural but diamagnetic Th3P4 and Th3As4 led to the conclusion that while the Th pnictides are indirect gap semiconductors the U compounds are metals due to the merging of the valence p band into the 6d conduction band; $electron interaction with the conduction bands is also indicated.186s187 Low-field measure- ments from 4.2 to 300 K of the magnetization of polycrystalline NpAs confirms the phase diagram with three antiferromagnetic phases although in high fields (> 5T) it behaves as a simple ferromagnet.*88 CmSi Cm,Si3 and CmSi were prepared by reacting CmF with the required amounts of Si in vucuo at 1260 "C (CmSi and CmSi2) and 1220 "C (Cm,Si,).CmSi is isomorphous with LaSi while Cm,Si and CmSi2 have /3-PuSi2- and a-ThSi2-type structures respectively. lS9 Th(S04)2*8H20 is monoclinic with Th in a ten-co-ordinated bicapped square antiprism. 190 On the other hand [NEt,],[Th( NCS)J has Th in eight-co-ordination in a strict cubic config~ration'~~ and Th(Moo4) has the structure of a true molybdate It with Th in a nearly regular square antipri~m.'~~ has been deduced that [NEt4],[UO2F(NO,),] has bidentate NO and bridging F-in the dinuclear anions but there is no clear evidence for electronic coupling between UO;+ groups.'93 The U in [C,HI4NO],[( U02),(NO,),(OH),] is eight-co-ordinated and double bridged by OH-.194 Two forms of the complex U02S04-20C(NH2), are obtained by evaporation of solutions of the components ; fast evaporation gives mainly the P-form (yellow) slow the a-form (green).In each form the U lies at the centre of a pentagonal bipyramid formed by 0;the equatorial 0 atoms are from SO',-(three) and urea (two). Bridging tridentate SO:-joins the bipyramids into double chains as in uranyl sulphate hydrates. Differences in chain packing are responsible for the two forms. 195 UO2SeO,.20C( NH,) is also composed of pentagonal bipyramidal chains of U polyhedra joined by tridentate bridges of SeO5- interbonded by H- bonds.196 Ortho and condensed phosphates of U have been reviewed.'97 Hydrated acid salts of UO;' containing HPOZ- and HASO:- are of interest because of proton conduc- tivity in the solid.Gel growth and characterization of HUO2AsO4-4H20 have been des~ribed.'~~ Phase transitions were observed at 260 and 290K in 2H(U02X04)-42H20 with X = P and As respectively. A 2H n.m.r. study on the solid indicated that in the high-temperature phases n.m.r. lineshapes are consistent 185 M. S. S. Brooks and P. J. Kelly Phys. Rev. Lett. 1983 51 1708. J. Schoenes M. Kueng R. Hauert and Z. Henkie Solid State Cornmun. 1983 47 23. 187 Z. Henkie W. R. Johanson A. J. Arko G.W. Crabtree and C. Bazan Phys. Rev. E Condens. Matter 1983 28 4198. 188 A. Blaise J. M. Fournier D. Damien and A. Wojakowski J. Magn. Mugn. Muter. 1983 31-34 233. F. Weigl and R. Marquart J. Less-Common Met. 1983 90,283. J. Habash and A. J. Smith Acta Cryst. Sect. C Cryst. Struct. Commun. 1983 C39 413. 191 P. Charpin M. Lance and A. Navaza Acta Cryst. Sect. C Cryst. Struct. Commun. 1983 C39 190. I92 T. L. Cremers P. G. Eller and R. A. Penneman Acta Cryst. Sect. C Cryst. Struct. Commun. 1983 C39 1165. '93 C.D. Flint and P. A. Tanner Polyhedron 1983 2 623. I94 B. Viossat Nguyen Huy Dung and C. Soye Acta Cryst.,Sect. C Cryst. Struct. Commun. 1983 C39,573. I95 J. Toivonen and L. Nunisto Inorg. Chem. 1983 22 1557. '96 V. E. Mistryukov and Yu.N. Mikhailov Koord. Khim. 1983 9 97. 197 L. V. Kobets and D. S. Umreiko Usp. Khim.,1983 52 897 (Chem. Abstr. 1983 99 46919). 198 E. Manghi and G. Polla J. Cryst. Growth 1983 61 606. Sc Y the Lanthanides and the Actinides 321 with fast chemical exchange of 2H between all the H-bond sites in the water layer with participation of all 2H.199 A powder neutron-diff raction study2'' of N2H4U02P04-32H20 has shown it to have a structure closely related to the proton conductor HU02P04-4H20 but without clear evidence for discrete NHZ. The room temperature structure of 2HU02As04.4H20 has H-disorder confined to the H-bond between oxygen within the squares of H20 molecules.201 Proton conductivity in HU02As04.4H20 determined below the transition temperature at 299 K led to the conclusion that conductivity probably occurs by the vehicle mechanism involving co-operative motion of H30+ and H20.202 Above 299 K proton conductivity is dependent on water content.203 Apart from preparative studies the chemistry of aqueous systems dominates solution work published this year.The solution chemistry of the An has been reviewed204 and compared205 with that of the Ln. Hydrolysis of ThIV in 0.1 M KN03 at 25 "C was investigated206 potentiometrically giving data best fitted by a model which assumes the species formed to be ThOH3' Th,(OH);l and Th,(OH):f. Ion-exchange and spectrophotometric studies of complex formation led to the conclusion207 that at <lo-' M UO',+ and from pH 2 to 5 only mononuclear hydroxy complexes are formed in 0.5 M NaNO at 20 "C.Hydrolysis of NpOl in the pH range 7 to 9 is discouraged by Cog-in solution.208 The solubility of U'" hydrous oxide in NaOH under reducing conditions was examined without obtaining evidence for amphoteric beha~iour.~'~ On the other hand wide angle X-ray scattering has provided evidence for cation-cation complex formation in concentrated solutions (-1.7 M) of UO',' + NpO; and of NpOZ alone.210 There is evidence for polaro- graphic reduction of Ac"' to Ac" in solutions containing 18-crown-6211 and for radiolytic reduction of Cf"' to Cf" from pulse radiolysis studies.212 Bk'" is extracted from HN03 by tri-n-octylphosphine oxide (TOPO) as Bk( N03)4-2TOP0213 and from H2SO4 by n-decylamine in CHC13 as (n-C 10H21 NH3)2 Bk( ; the latter extraction enables Bk to be separated from transplutonium"' and Ln"' species.214 A good deal of interest centres on carbonate complexes.AH determined2" calorimetrically at 298 K is -3085.5 kJ mol-' for UO2(CO3):-. Redox equilibria between Uv' and UIV in 3 M NaClO at total [U] between loA3 and M [H+] from to lo-* and Pco,from 0.02 to 0.1 atm are explained by equation 5 with I99 T. K. Halstead N. Boden L. D. Clark and C. G. Clark J. Solid State Chem. 1983 47 225. A. N. Fitch and B. E. F. Fender Acta Cryst. Sect. C Cryst. Struct. Commun. 1983 C39 162. A. N. Fitch L. Bernard A. T. Howe A. F. Wright and B. E. F. Fender Acta Cryst. Sect. C Cryst. Struct. Commun. 1983 C39 159. 202 K. D. Kreuer A. Rabenau and R. Messer Appl. Phys.A 1983 32 45. 203 K. D. Kreuer A. Rabenau and R. Messer Appl. Phys. A 1983 32 155. 204 G. R. Choppin Radiochim. Acta 1983 32 43. 205 G. R. Choppin J. Less-Common Met. 1983 93 323. 206 P. L. Brown J. Ellis and R. L. Sylva J. Chem. SOC.,Dalton Trans. 1983 31. 207 Yu. P. Davydov and V. M. Efremenkov Zh. Neorg. Khim. 1983 28 2316. 208 L. Maya Znorg. Chim. 1983 22 2093. '09 J. L. Ryan and D. Rai Polyhedron 1983 2 947. 210 B. Guillaume R. L. Hahn and A. H. Narten Znorg. Chem. 1983 22 109. 211 Y. Yamana T. Mitsugashira Y. Shiokawa A. Sato and S. Suzuki J. Radioanal. Chem. 1983 76 19. 212 J. C. Sullivan L. R. Morss K. H. Schmidt W. A. Mulac and S. Gordon Znorg. Chem. 1983,22,2338. 213 D. A. Malikov M. S. Milyukova B. F. Myasoedov and E.V. Kuzovkina Radiokhimiya 1983,25,305. 214 D. A. Malikov M. S. Milyukova E. V. Kuzovkina and B. F. Myasoedov Radiokhimiya 1983,25,313. 215 0.A. Devina M. E. Efinov V. A. Medvedev and I. L. Khodakovskii Geokhimiya 1983 677 (Chem. Abstr. 1983. 99 59743). 322 S. J. Lyre Eo = -0.279V.216 Some evidence for a Uv complex was obtained and explained in a subsequent paper217 in which it is concluded that the complex anion is U02 (CO,)s-. Values for the apparent normal potentials of the couples AmV'/ AmV and uO,(CO,):-+ 2e + 2~0,(g) eu(co,)~-(5) Am'"/Am"' in NaHC0 + Na2C03 of total concentration 1.2 to 2.3 M were obtained by potentiometric titration with ferrocyanide. While the AmV'/ AmV couple (0.975 V) is independent of [CO$-] that of Am'V/Am'l' decreases as [CO:-] increases (0.924 V at 1 M COi-).218 Raman spectra of An" and An"' complexes in 2 M Na2C03 for An = Np Pu,or Am have features which relate to the charge-transfer bands in the electronic spectra and to the formal potentials of the AnV'/AnV couples.219 Ther- modynamic or conditional equilibrium constants have been reported for various phosphate complexeszz0 of UOi+ for 1 1 complexes of ThIV with oxydiacetate iminodiacetate thiodiacetate and succinate,221 and for ThIV and UO',+ reactions with several a-amino acids.z2z An"' forms azide (N;) complexes with formation constants that are an order of magnitude greater than those for Ln"'.However ''N n.m.r. and other spectroscopic studies suggest that both An and Ln form inner complexes.223 Electrochemical reduction of U(acac) to U(acac) 4 in propylene carbonate and MeCN at a Hg cathode proceeds in two steps involving the formation of the intermediate U(acac); by ligand exchange.224 Adducts of UO,(tfa) and U02(ptfa) with DMSO and (Me2N)3P0 (Htfa = trifluoroacetylacetone and Hptfa = pivaloyltrifluoroacetone) are said to be stable in the vapour phase.225 A vapour-phase study of adducts of UO,(tfa) with (MeO) PO (BuO) PO (MeO)2MeP0 and Me PO has shown that volatility decreases with increasing chain length and increasing polarity of the neutral ligand.2z6 It has been found for 15 adducts of U02(hfa)2 in solution and vapour phases (Hhfa = hexafluoroacetylacetone) that i.r.transition-frequencies for the UO;' and hfa- moieties as well as I3C and 'H n.m.r.shifts correlate linearly with the relative basicity of the add~ct.~~~ However it emerged from spectra of UOz(hfa)2 adducts with THF DMSO and (Me0)3P0 that the U02 symmetric stretch in the THF adduct possessed anomalously high i.r. intensity which was ascribed to perturbation of the U02 by interactions with the a-CH2 group of the adduct.228 In solid [Me,N][UO,(hfa),.X] where X = C1- Br- or N; the structures are similar with U in a pentagonal bipyramidal arrangement of four 0 atoms from ligands and *I6 L. Ciavatta D. Ferri I. Grenthe F. Salvatore and K. Spahiu Inorg. Chem. 1983 22 2088. 217 D. Ferri I. Grenthe and F. Salvatore Inorg. Chem. 1983 22 3162. 218 J. Y. Bourges B. Guillaume G. Koehly D. E. Hobart and J. R. Peterson Inorg.Chem. 1983,22 1179. 219 C. Madic D. E. Hobart and G. M. Begun Inorg. Chem. 1983 22 1494. 220 M. Markovic and N. Paukovic Inorg. Chem. 1983 22 978. 22 1 P. Di Bernado A. Cassol G. Tomat A. Bismondo and L. Magon J. Chem. Soc. Dalton Trans. 1983 733. 222 M. Nowmand and N. Meissami 1. Chem. SOC.,Dalton Trans. 1983 1529. 223 C. Musikas C. Cuillerdier J. Livet A. Forchion and C. Chachaty Inorg. Chem. 1983 22 2513. 224 E. Graf A. Giraudeau and M. Gross Inorg. Chem. 1983 22 3233. 225 G. V. Sidorenko and D. N. Suglobov Radiokhimiya 1983 25 413. 226 G. V. Sidorenko D. N. Suglobov and K. G. Golodova Radiokhimiya 1983 25 418. 227 R. G. Bray and G. M. Kramer Inorg. Chem. 1983 22 1843. 228 R.G. Bray Spectrochim. Acta Part A 1983 39 559.Sc Y the Lanthanides and the Actinides 323 the X group in the equatorial plane.229 The U stereochemistry is similar in U02(dpm),.MeOH (Hdpm = dipi~aloylmethane).~~' U(dbm) is isostructural with Ce(dbm),; the metal is eight-co-ordinated to oxygen in a near perfect square antiprism with the ligands spanning opposite square faces.23' The U"' crown ether complexes UC1 L2 (L = benzo- 15-crown-5 or 18-crown-6) UC13( cyclohexyl- 15-crown-5) (UC13)5 (dibenzo- 18-crown-6) (UCl,),( cis-syn-cis-dicyclohexyl-18-crown-6),,have been prepared from UCl + crown ether in MeCN or MeCN-propanoic acid by Zn( Hg) reduction.232 In solid Th(DMF)(C9H6N0), the 8-quinolinolate ligands are bidentate and the DMF monodentate and bonded through oxygen; the co-ordination polyhedron of Th is that of a slightly distorted tricapped prism.233 Th is also nine-co-ordinated in [Th(0da)(S0,)~.2H,O]-H~0 where oda = oxydiacetate but in a monocapped square antiprismatic geometry in which both oda and SO:-are shared between Th in a polymeric network.234 Crystal structure determinations of octamethylpyrophosphoramide(ompp) adducts of ThCI and U(NCS)4 show them to be ThCl,(ompp) and U(NCS),(ompp) with each metal eight-co-ordinated to four unidentate and two bidentate (ompp) ligand~.~,~ A reaction product of UCl and DMF in acetone can be represented as [UCl( DMF)7]2[U02C14]3 in which the U'" in the cation is eight-~o-ordinated~,~ while in U(NCS),(OP(NMe2),} the U is also eight-~o-ordinated.~,~ There is a distorted octahedral array of ligands around U in UBr4.2Ph3P0 with the Ph3P0 co-ordinated in trans positions.238 Two complexes of UO',+ with di-n-butylphos- phoric acid (X) and tri-n-butylphosphine oxide (Y) used as liquid-liquid extractants have been isolated and analysed by X-ray methods they were [U02.X2], and a mixed dimeric complex [OU2.X.Y.NO3l2.In each structure pairs of linear UO:+ are bridged by 2X- but in one case the bridging is repeated indefinitely while in the other it is terminated by NO and Y ~o-ordination.~,~ In [U02(DMSO)5][C104]2 the dioxouranium(v1) group is surrounded in the equatorial plane by the five 0 atoms from the DMSO ligand~.~~' The Schiff base derived from heptane-2,4,6-trione- 1 -(o-hydroxypheny1)butane- 1,3-dione and 1,2-diarninoethane has available dis- similar adjacent donor sets (N202 and 0202).241 isomer is found Only the 0202 for UO$+.Treatment of (q5-C5H5),UC1 in MeCN with gaseous butadiene (X) and traces of O2 gives a green solid best written as [( v5-CS H5),U( NCMe)2]2[U02C14].2X.242 229 L. Prasad E. J. Gabe B. Glavincevski and S. Brownstein Acta Cryst. Sect. C' Cryst. Struct. Commun. 1983 39 181. 230 P. I. Mackinnon and J. C. Taylor Polyhedron 1983 2 217. 23 1 D. L. Kepert J. M. Patrick and A. H. White J. Chem. SOC.,Dalton Trans. 1983 567. 232 F. A. Hart and M. Tajik Inorg. Chim. Acta 1983 71 169. 233 R. J. Barton R. W. Dabeka Hu Shengzhi L. M. Mihichuk M. Pizzey B. E. Robertson and W. J. Wallace Acta Cryst. Sect. C Cyst. Struct. Commun. 1983 39 714. 234 R.Graziani G. A. Balliston V. Casellato and G. Sbrignadello J. Chem. Soc. Dalton Trans. 1983 1. 235 D. L. Kepert J. M. Patrick and A. H. White J. Chem. Soc. Dalton Trans. 1983 559. 236 D. L. Kepert J. M. Patrick and A. H. White J. Chem. Soc. Dalton Trans. 1983 381. 237 D. L. Kepert J. M. Patrick and A. H. White J. Chem. Soc. Dalton Trans. 1983 385. 238 G. Bombieri F. Benetollo K. W. Bagnall M. J. Plews and D. Brown J. Chem. Soc. Dalton Trans. 1983 343. 239 J. H. Burns Inorg. Chem. 1983 22 1174. 240 J. McB. Harrowfield D. L. Kepert J. M. Patrick A. H. White and S. F. Lincoln J. Chem. SOC.,Dalton Trans. 1983 393. 24 I J.-P. Costes and D. E. Fenton J. Chem. SOC.,Dalton Trans. 1983 2235. 242 G. Bombieri F. Benetollo E. Klahne and R.Dieter Fischer J. Chem. SOC.,Dalton Trans. 1983 11 15. 324 S. J. Lyle Although the (CH3),C co-ordination is unexceptional in Th[q5-(CH3),C5I2-[CH2Si(CH3)& the Th[CH2Si( CH3)3]2 fragment is highly unsymmetric exhibiting intramolecular non-bonded contacts whereby a methyl H of one ligand approaches within 2.3 A of the a-C of the other.243 In (q5-C5H5)3UCHP(CH3)2Ph and (77,-C5H5)3U'.THF the U is bound in a tetrahedral fashion to three C5H5 ligands and the CHP(CH3)2Ph or THF ligand,244.245 whereas in Ph,As[( q5-C5H5)3U(NCS)2] the co-ordination about the U is trigonal bipyramidal with three 7r-bonded C5H5 rings in the equatorial plane and two N-bonded NCS- in the axial positions.246 In indenyluranium trichloride bis(tetrahydrofuran) the co-ordination geometry about U is pseudo octahedral with one q5-C9H ligand and one THF occupying trans axial positions and the other ligands in equatorial positions.247 It has been concluded from a study of the photoelectron spectra of (ind),LnX where ind = indenyl Ln = Th or U and X = C1 Br MeO or Me that the Ln-ind bonding is similar to that in corresponding C5H5 complexes but that there is evidence for greater 5f covalency in the former.248 Photoelectron spectra of a series of alkyl substituted uranocenes indicate that both metal 5f and 6d orbitals participate in ring-metal bonding which appears to increase in strength with increasing alkylation of the cy~lo-octatetraene.~~~ 237Np Mossbauer spectra were taken for a series of Np'" compounds of general compositions NpX, NpX2Y2 and NpX2YY' where X = acac bis( 1-pyrazolyl)borate tris( 1-pyrazolyl)borate; Y,Y' = C1 C5H5 or (CH3)J5.Comparison of isomer shifts did not provide evidence for covalent bonding between the potentially .rr-bonding ligands and Np. Ligand repulsion preventing metal-C H5 or (CH,),C orbital overlap was proposed as the e~planation.~~' 243 J. W. Bruno T. J. Marks and V. W. Day J. Organornet. Chem. 1983 250 237. 244 R. E. Cramer. R. B. Maynard J. C. Paw and J. W. Gilje. Organometallics 1983 2. 1336. 245 H.J. Wasserman A. J. Zozulin D. C. Moody R. R. Ryan and K. V. Salazar J. Organomet. Chem. 1983 254 305. 246 G. Bombieri F. Benetollo K. W. Bagnall M. J. Plews and D. Brown J. Chem. SOC. Dalton Trans. 1983 45. 247 J. Rebizant M.R. Spirlet and J. Goffart Acta Cryst. Sect. C:Cryst. Struct. Commun. 1983 39 1041. 248 I. L. Fragala J. Goffart G. Granozzi and E. Ciliberto Znorg. Chem. 1983 22 216. 249 J. C. Green M. P. Payne and A. Streitwieser jun. Organometallics 1983 2 1707. 250 D. G. Karraker Znorg. Chem. 1983 22 503.

ISSN:0260-1818    

DOI:10.1039/IC9838000305

出版商:RSC    

年代:1983

数据来源: RSC

摘要:

13 Radiochemistry By D. S. URCH Chemistry Department Queen Mary College London El 4NS 1 Introduction Radiochemical techniques and procedures are used in most branches of chemistry; a review of recent progress in radiochemistry must therefore be selective if it is not to cover too wide an area and to repeat consideration of topics covered on other sections of Annual Reports. The topics that will form the main sections of this review are those where radioactivity would seem to be of prime importance (i) the production of specific radioactive isotopes (ii) the synthesis of labelled molecules and (iii) chemical reactions initiated by nuclear transformations (but excluding radiation chemistry). The safety aspects of radiochemistry will also be considered. But the inorganic chemistry as opposed to the radiochemistry of the heavy radioac- tive elements is more conveniently considered elsewhere in this Report.Perhaps however some recent reviews should be noted on the chemistry of polonium’ and of and the appearance of four Gmelin supplements for uranium (solvent e~traction,~ compounds with Group V elements and germanium,’ ion exchange and chromatography,6 and the analytical chemistry of uranium7) and two general articles on the transuranium Other reviews of transuranium chemistry have considered lower lo and higher’ oxidation states the solution chemistry of the actinides,I2 and the prod~ction’~ and chemistryI4 of the trans-plutonium elements. ’ K. W. Bagnall Radiochim. Acta 1983 32 153. ’ L. Stein Radiochim.Acta. 1983 32 163. V. V. Avrorin R. N. Krasikova V. D. Nefedov and M. A. Toropova Vsp. Khim. 1982 51 23. 2. Kolarik ‘Uranium Supplement D2’ Gmelin Handbook of Inorganic Chemistry Springer Berlin 1982. D. Brown P. E. Potter and H. Wedemeyer ‘Uranium Supplement C14’ Gmelin Handbook of Inorganic Chemistry Springer Berlin 1982. H.0. Haug J. Schoen Y.Marcus and S. Specht ‘Uranium Supplement D4’ Grnelin Handbook of Inorganic Chemistry Springer Berlin 1983. ’ E. Gantner E. Mainka H. Ruf H. Wertenbach H. Schieferdecker and A. Seidel. ‘Uranium Supplement A7’ Gmelin Handbook of Inorganic Chemistry Springer Berlin 1982. ’G. T. Seaborg Am. Sci. 1980 68 279. G. T. Seaborg Sci. Quesr 1980 53,7. lo N.B. Mikheev Radiochim Acta. 1983 32 69. ‘I V.I. Spitsyn Izv. Akad. Nauk SSSR Ser. Khim. 1982 731. ’’G. R. Choppin Radiochim. Acta 1983 32 43. l3 ‘Review of the accomplishments and promise of US transplutonium research 1940-8 l’ (DGE/ER/ 10984- 7) ed. 0. L. Keller R. G. Wymer Nat. Academy of Sciences Washington U.S.A 1982. l4 E. K. Hulet Radiochim Acta 1983 32 7. 325 326 D. S. Urch A major multi-author treatise on radiochemistry has appeared in CzechlSa and also in a German’5b3‘ translation which covers all aspects of nuclear chemistry. At a more practical level is the ‘Radiochemical Laboratory Course’ in which basic radiochemical techniques are described.I6 The more sophisticated separation methods that are required for low-level radioactive measurements and environmental analysis” have also been reviewed.The recently published ‘Radiation Data Base’ is a mine of useful information” on half-lives decay schemes etc. but is in Japanese a less ambitious listing has also appeared in Portuguese.” Reactor Chemistry and Reactor Engineering20,2’ are subjects of a recent report and book respectively. The radiochemistry associated with nuclear explosions the formation of heavy isotopes local hot-atom reactors production of radioactive liquids and gases etc. has been considered in some Finally a new and rather exciting development in radiochemistry is the use of the radiation from naturally occurring trace isotopes to pin-point specific mineral grains in complex mineralogical phases or specific sites in full cell elements and on catalyst surfaces the so called ‘nuclear mi~roprobe.~~ 2 Radioisotopes In this section methods for the production of specific radioisotopes will be reviewed.Tritium 3H.-Tritium is easily produced by the thermal neutron irradiation of lithium [6Li(n a)3H]; if this reaction is carried out in lithium-doped aluminium on silica the tritium is captured presumably as -03H. The tritium can be released either by strong heating (>300”C) or it has been found,24 by an exchange reaction with ethylene. Much concern has recently been shown in methods to separate tritium from hydrogen gas (an anticipated problem in fusion systems) and from water (in swimming pool reactors). For hydrogen gas the methods investigated have included thermal diff u~ion,~~,~~ the use of zeolites (NaX-3 M)27or molecular sieves,28 occlusion by lamellar potassium graphite,29i30 and diffusion through metal films (palladium3’ and uranium32).The catalytic oxidation of tritium as a way of removing it from Is (a) V. Majer J. Cabicar V. Cernik V. Kacena J. Stary K. Svoboda and A. Zeman ‘Foundations of Nuclear Chemistry-Zaklady jaderne chemie’ Prague Czechoslovakia 1981 ;(b) ibid. German translation J. A. Barth Leipzig 1982 (c) ibid, German translation Hauser Munich 1982. l6 R. Schwanker ‘Einfuehrung in das kern- und radio-chemische Grundpraktikum’ Schoeningh Paderborn BDR 1980. W. S. Lyons Radiochem. Radioanal. Lett. 1982 53 259. ” ‘Radiation Data Book’ ed. Y. Murakami A. Danno M. Kobayashi Chijin Shokan Tokyo Japan 1982. l9 C. H. Collins J. C. de Andrade and K.E. Collins Quim. Nou. 1981 4 57. 20 E. Akatsu ‘Fundamentals of Reactor Chemistry’ (JAERI-M-9827) Jap. Atomic Energ. Res. Inst. Tokyo Japan 1981. 21 M. Benedict H. Levi and T. Pigford Nucl. Sci. Eng. 1982 82 476. 22 A. S. Krivokhatskij Radiokhimiya 1982 24 277. 23 C. J. Maggiore T. M.Benjamin D. S. Burnett P. J. Hyde P. S. Z. Rogers S. Srinivasan T. Tesmer and D. S. Woolum IEEE Trans. Nucl. Sci. 1983 30 1224. 24 M. Matsuyama and T. Takeuchi J. Nucl. Sci. Technol. (Tokyo) 1981 18 15. 25 A. Kitamoto K. Hisajima and Y. Takashima in ‘Symposium on the separation of deuterium and tritium’ ed. M. Shimizu and S. Isomura Gakkai Shuppan Senta Tokyo Japan 1982 p. 67. 26 0. Takayasu I. Makino S. Yamagami and T. Takeuchi Bull. Chern. SOC.Jpn.1982 55 1238. 27 A. S. Polevoj and I. P. Yudin Zh. Fiz. Khim. 1982 56 2015. 28 F. Ono Y. Takahashi and M. Nakazawa re$ 25 p. 121. 29 T. Terai and Y. Takahashi Nucl. Sci. Technol. (Tokyo) 1981 18 643. 30 Y. Takahashi T. Terai and M. Kanno re$ 25 p. 131. 31 H. Fujita K. Fujita H. Sakamoto and K. Higashi re$ 25 p. 157. 32 S. Imoto T. Tanabe K. Utsunomiya reJ 25 p. 151. Radiochemistry 327 helium has proved ~uccessfu1,~~ although the development of suitable techniques to facilitate exchange between hydrogen gas and water proved more difficult.34 Molecular sieve 4A gave good results35 in isotopic separation of various isotopic water molecules (as steam) e.g. 'H3H0 and 3H20. Such approaches will be helped by the measurement of vapour pressures of a range of small molecules (H2 H20 NH3)36of different isotopic composition.Laser techniques have also been employed to separated tritium-labelled molecules ; C3HF3 proved a suitable 'Be.-Although this isotope is normally produced by proton or deutron bombardment of lithium-6 or boron-10 respectively it is possible to make small amounts of 'Be by the thermal neutron irradiation of lithium utilizing the secondary nuclear reactions brought about by the recoil trition~~~ thus:- 6Li(n a)3H 6Li(3H 2n)7Be. 32Si.-A method for the production of 32Si by bombarding lithium sulphate with 51 MeV protons [34S(p 3~)~~Sil has been described.39 First Row Transition Elements.-Both 52Fe and 52Mn are produced by the bombard- ment of nickel targets with 800 MeV protons:40 separation is effected with an ion exchange resin; techniques for the preparation of high purity "Fe have also been rep~rted.~' 6SZn can be separated efficiently and cleanly from tin and bismuth by amalgam formation and electr~lysis.~~ 63Zn (T,,~= 38.1 minj a positron emitter can now be easily produced43 on small cyclotrons using the 63Cu(p-15 MeV n)63Zn reaction.Ga.-Problems associated with the preparation of this isotope from zinc targets enriched in 68Zn have been con~idered.~~ The production of 68Ga from tin oxide has been Br.-Bromine-75 which would appear to be the most suitable bromine isotope for use in nuclear medicine46 can be prepared from krypton-78 by b~mbardment~~ with quite low-energy protons [78Kr(p-l 5MeV a j75Br].Methods for the purification of 33 T. Abe K. Tsukumo M. Fukuhara T. Suzuki and S. Okazaki FAPlC (Tokyo) 1981 97 24. 34 Y. Asakura H. Yusa and H. Yamashita re$ 25 p. 31. 35 S. Tanaka and R. Kiyose ref 25 p. I I 1. 36 S. M. Dave S. K. Ghosh and H. K. Sadhukhan (BARC-I 168) Report Bhabha Atomic Research Centre Bombay India 1982. 37 Y. Makide S. Hagiwara 0.Kurihara K. Takeuchi and Y. Ishikawa reJ 25 p. 179. 38 K. Sakai Tokai Daigaku Kiyo Koga Kuba 1981 39. 39 L. Linder and P. Polak Radiochim. Acta 1982 31 23. 40 H. A. O'Brien jun. P. M. Grant G. E. Bentley J. W. Barnes and H. M. Zacharis J. Labelled Comp. Radiopharm. 1982 19 1366 4' A. 1. Egorov B. A. Morozov A. F. Ivanchenko G. I. Karazhanova and A. V. Safonov Radiokhimiya 1982 24 262." R. Gok and E. Edguer Turk. J. Nucl. Sci. 1982 9 108. 43 R. E. Bigler J. R. Dahl L. S. Rothman and P. B. Zanzonico J. Labelled Comp. Radiopharm. 1982 19 1429. 44 R. D. Fin J. P. Dwyer K. K. Koh A. Rodon Y. Sheh J. S. Sinnreich and P.M. Smith J. Labelled Comp. Radiopharm. 1982 19 1340. 45 Y. Yano and T. F. Budinger J. Labelled Comp. Radiopharm. 1982 19 1441 46 A. M. J. Paans T. Wiegman W. Hoeve and W. Vaalburg Nucl. Geneeskd. Bull. 1982 4 130. 47 A. M. Friedman 0.J. De Jesus P. Harper and C. Armstrong J. Labelled Comp. Radiopharm. 1982 19 1427. 328 D. S. Urch bromine-77 (from the selenium target where it is made by proton bombardment) have been described.48 Kr.-77Kr can be prepared by 3He bombardment of a selenium target.49 82Rb.-This positron emitter can be eluted from a column containing adsorbed 82Sr.45 Second Row Transition Elements.-Technetium continues to command most attention in this area from methods to purify the molybdenum from which it will be made5' to optimizing the condition for its separation from m~lybdenum.~' Protons (1 5 MeV) [92M0(p n)92Te] can be used to produce lighter technetium isotopes.52 But much higher proton energies (67.5 MeV) have to be used to get 97R~ The from 101Rh.53 extraction of "'Ag from hydrochloric acid can be effected54 with di-n-pentyl or di-n-octyl sulphoxide.115m In.-This isotope can be prepared when required by elution from an ion-exchange resin carrying ' ''Cd.55 1.-The production of the favoured 1231isotope by the following reactions has been described '24Te(p 2n)'231,56 12'Sb(a2n)'231,57 123Xe decays8 and the possibility of initiating 124Xe( 'y n)'23Xe(EC/3)'231 by means of 25 MeV bremsstrahlung has been ~onsidered.~~ An 1221 generator utilizing '22Xe decay has also been described.45 lBCs.-This isotope can be made in a 'generator' as well,45960 from the decay of 128Ba which had been produced by 132Cs(p 6n)128Ba.172 Lu.-This isotope can be separated from its long-lived parent '72Hf by solvent extraction.61 178 W.-Chromatography was the preferred technique for separating 17*Wfrom the parent 178Ta.62 19'Ir.-40 MeV ?-Irradiation of platinum (198) gave rise to two isomeric forms of I9'Ir with half-lives of 6.1 and 8.9 minutes.63 48 Z.B. Alfassi J. Radioanal Chern. 1983,76 325. 49 G. Blessing K. Suzuki H. Youfeng S. M. Qaim and G. Stocklin J. Labelled Cornp. Radiopharrn. 1982 19 1431. S. A. Ali and H. J. Ache J. Labelled Cornp. Radiopharrn. 1982 19 1439. 5' M. Molter D. Puetter and A. G. Hoechst German (BRD) Patent 2906439/A 1980. 52 R. M. Lambrecht and S. M. Montner J. Labelled Comp. Radiopharrn. 1982 19 1434. 53 M. C. Lagunas-Solar M. J. Avila N. J. Navarro and P. C. Johnson J. Labelled Cornp. Radiopharrn. 1982 19 1436. 54 A. S. Reddy M. L. Reddy and B. R. Reddy Radiochern. Radioanal. Lett. 1983 55 227. s5 G. J. Ehrhardt W. Volkert W. F. Goeckeler and D. N. Kapsch J. Nucl. Med. 1983 24 349. 56 G. Goin J. Vernois C. Cimetiere and J. Leger in 'International Conference on cyclotrons and their applications' Les Editions de la Physique Les Ulis France 1982 p.697. 57 L. Yongjian S. Qixun S. Degun et a/. J. Labelled Cornp. Radiopharrn. 1982 19 1358. 58 J. W. Barnes M. A. Ott K. E. Thomas P. M. Wanek G. E. Bentley F. J. Steinkruger and H. A. O'Brien jun. J. Labelled Cornp. Radiopharrn. 1982 19 1432. 59 A. B. Malinin V. T. Kharlamov N. V. Kurenkov and V. B. Popovitch J. Labelled Cornp. Radiopharrn. 1982 19 1360. 60 M. C. Lagunas-Solar F. E. Little and H. A. Moore J. Labelled Cornp. Radiopharrn. 1982 19 1450. 61 P. M. Grant R. J. Daniels W. J. Daniels G. E. Bentley and H. A. O'Brien jun. J. Radioanal. Chern. 1983 76 319. 62 R. D. Neirinckx A. Le Blanc M. Vogel J. Trumper J. L. Lacy and P.C. Johnson J. Labelled Cornp. Radiopharrn. 1982 19 1447. 63 D. W. Anderson H. Issaian and R. F. Petry Med. Phvs. 1982 9 340. Radiochemistry 329 3n) produces 195Hg Au.-Proton bombardment of gold 197A~(p 64 which can be used as a convenient source of 195A~ for nuclear medicine. The quality control of 198Au has also been con~idered.~’ T1.-The chemistry of thallium relevant to the production of 203Tl has been described;66 this isotope is of interest as precursor of 201T1.Another way of producing this isotope is by the decay of 201Pb67 (produced by 24 MeV proton bombardment of natural thallium). The lead and thallium can be separated by ion exchange. Heavy Radioactive Elements.-Ion exchange methods for separating 210Pb,68*69 210gi68,69 and 210p068,70 have been described whereas a liquid-liquid two-phase extraction7’ process was used to purify 228Ac.Solvent extraction was also used to purify 227Ac.72 Techniques for the production of gram amounts of protoactinium metal have been described.73 Chr~matography,~~ and the liquid-liquid e~traction,~~ formation of crown-ether complexes76 have all been used in the purification of uranium. The optimum conditions for separating 239Np from 243Am77 and for the recovery of americium78 using chromatographic methods have been described. 3 Labelled Compounds One of the most important and fastest growing areas for the production of labelled compounds and for the development of new techniques for producing them continues to be that of radiopharmaceuticals for use in nuclear medicine -both diagnostic and therapeutic.This field of activity has been reviewed considering the especial problems of producing compounds labelled with short-lived isotope~~~-~l and the relationship between structure and activity in radioactive compounds.8z It has also been the subject of many international conference^^^-^^ as well as a dominant 64 R. Bett J. G. Cuninghame H. E. Sims and W. H. Willis J. Labelled Comp. Radiopharm. 1982 19 1444. 65 H. El-Asrag S. El-Bayoumy and E. Hallaba Arab J. Nucl Sci. AppL 1981 14 253. 66 H. H. Caudill H. R. Gwinn and L. E. McBride Nucl. Instrum. Methods Phys. Res. 1982 200 145. 67 A. M. S. Braghirolli MSc Thesis University of Rio de Janeiro Brazil 1981 Atomindex INIS-BR-07.68 R. A. Pacer J. Radioanal. Chem. 1983 77 19. 69 D. K. Bhattacharya and A. De J. Radioanal. Chem. 1983 76 109. 70 V. R. Casella C. T. Bishop A. A. Glosby M. H. Hiatt N. F. Mathews L. A. Bunce and P. B. Hahn Radiochem. Radioanal. Lett. 1983 55 279. 7’ J. R. Noyce J. M. R. Hutchinson and W. A. Kolb J. Radioanal. Chem. 1983 79,5. 72 A. I. Mikhajlichenko E. G. Goryacheva N. M. Aksenova and A F. Denisov Radiokhimiya 1982,24 207. 73 J. C. Spirlet E. Bednarczyk and W. Mueller J. Less-Common Metals 1983 92 L27. 74 Y. Sakuma M. Okamoto H. Kakihana J. Nucl. Sci. Technol. (Tokyo) 1981 18 793. 75 B. V. Stamicarbon Netherlands Patent No. 8000832/A 1980. 76 A. M. Rosen Z. I. Nikolotova N. A. Kartasheva A. G. Luk’yanenko and A. V. Bogatskij Dokl.Akad. Nauk SSSR 1982 263 1165. 77 P. D. Wilson J. Less-common Metals 1983 91 L13. 78 W. I. Yamada L. L. Martella J. D. Navratil J. Less-common Metals 1982 86 21 I. 79 S. Tazawa and Y. Nishihara Sumitomo Jukikai Giho 1982 30 76. no G. J. Uhlenhut H. Koch P. Kopecky and K. Svoboda Report of the Central Institute for Isotope and Radiation Research Leipzig Akad der Wissenschaften der DDR Leipzig DDR 1982 p. 37. ” J. S. Fowler and A. P. Wolf Report BNL-31222 Brookham Nat. Lab. Upton N.Y. U.S.A. 1981. 82 ‘Radiopharmaceuticals Structure-Acitivity Relationship’ ed. R. P. Spencer Grune and Strutton New York U.S.A. 1981. 83 ‘Radiopharmaceuticals 11 Proc. 2nd Int. Syrnp. Radiopharm.’ Society for Nuclear Medicine ed. V. J. Sodd D. R. Allen D.R. Hoogland and R. D. Ice New York U.S.A. 1980. 134 S. S. Zoghbi M. L. Thakur A. Gottschalk S. Pande S. C. Srivastava and P. Richards Report BNL-31282 Brookham Nat. Lab. Upton N.Y. U.S.A. 1982. 85 Proceedings of the 4th International Symposium on Radiopharmaceutical Chemistry J. Labelled Comp. Radiopharm. 1982 19 (issues 11 and 12). 330 D. S. Urch feature of many laboratory report^.'^-'^ The problems of radiochemical purity especially associated with autoinduced radiation damage have been considered in general'' and in particular for 34C,92 81Kr,93and ""'TC.'~~~ It is not however the purpose of this section of the report to consider this particular field in any depth nor to list every new synthesis of a labelled compound but rather to attempt just an overview of recent developments in labelling methods.3H-Tritium.-The chemistry of tritium is the subject of a recent Japanese and more specifically methods for making poly-tritiated molecules have been reviewed." A popular method for the production of tritium-labelled compounds continues to be by exposure to tritium gas but usually in the presence of a catalyst such as PdO {r3H]rnethyl-5-hydroxyyluracil and -thymine,98 [7,8,19,20-3H]naloxone,99 gonadotropin,"' and steroids'"} although it has been reported that side effects can be reduced by using a low pressure of tritium gas;'02 attempts at 'normal' Wilzbach labelling of insulin gave negative result^."^ A micro-wave dis- charge can also be used to induce tritium labelling;lo4 the presence of a methine site is found to be advantageous.Another popular method of labelling is catalytic halogen-tritium exchange (e.g. rnianse~in,'~'porcine dynorphin (1-17),Io6 [1,7,8-3H]dihydromorphine,'07 [5-3H]uraci1,'08 [6-3H]uraci1,'09 tamoxifen'" etc.). Other methods include exchange with labelled water"' ([ 15-3H]gibberellin-A3) and the 86 D. Comar in '9th Int. Conf. on cyclotrons and their application'-ed. G. Gendreau Les Editions de la Physique Les Ulis France 1982 p. 645. n7 E. I. Mikerin At. Ehnerg. 1982 (August) 89. an 'Radiochemistry Division annual report 1980' (BARC-I 160) ed. N. C. Jayadevan and S. B. Manohar Bhabba Atomic Research Centre Bombay India 1982. 89 A. G. de Silva 0. F. Lemos J. L. 0.de Britto J. A. Osso M. A. V. Bastos A.M. S. Braghirolli D. F. S. Chamma G. W. A. Newton and R. Weinreich Atomindex 1982 INIS-mf-7885. 90 (a) G. W. Kabalka 'Report on Nuclear Medicine' 1980-1982' (DOE/EV/ 10363-4) University of Ten- nessee Knoxville U.S.A. 1983; (b) G. W. Kabalka 'Progress Report on Nuclear Medicine 1982-1983' (DOEIEVJ 1063-3) University of Tennessee Knoxville U.S.A. 1983. 91 W. J. Welsh 'Guidelines for radiopharmaceutical quality control in hospitals' (EHD-8 1 -77) Department of National Health and Welfare Ottawa Canada 1982. 92 B. F. H. Drenth and R. A. de Zeeuw Inr. J. App. Radiar. Isor. 1982 33 681. Y3 M. Comet J. Croize M. Gautley J. P. Mathieu C. Pernin F. Dubois A. Verain J. Godart and J. Boutet J. Eiophys. Med. Nucl. 1982 6 121. 94 S. Vallabhajosula S.J. Goldsmith and H. Lipszyl J. Labelled Comp. Radiopharm. 1982 19 1565. 9s A. Yokoyama and K. Horiuchi in 'Proc. 3rd Int. Radiopharmaceutical Dosimetry Symposium' (FDA-8 1-8166) ed. E. E. Watson A. T. Schlafke-Stelson J. L. Coffey and R. J. Cloutier Bureau of Radiological Health Rockville Md. U.S.A. 1981. 96 'Chemistry of Tritium from Basics to Application' Atomic Energy Society of Japan Tokyo Japan 1982. 97 F. Cacace M. Speranza A. P. Wolf and R. Ehrenkaufer J. Labelled Comp. Radiopharm. 1982 19,905. 9n J. Filip and L. Bohacek Czechoslovak Patent 192238/B 1981. 99 G. Toth F. Sirokman M. Kramer A. Borsodi and A. Ronai J. Labelled Comp. Radiopharm. 1982 19 1021. loo E. Klauschenz M. Bienert H. Egler U. Pleiss H. Niedrich and K. Nikolics Peptides (Fayetteville N.Y.) 1981 2 445.101 J. Protiva E. Klinotova J. Filip and R. Hampl Radiochem. Radioanal. Lett. 1982 53 277. 102 H. Pluciennik and J. Hrebenda Radiochem. Radioanal. Lett. 1983 56 25. Io3 J. Uschkoreit D.Sc. Dissertation Tech. Hoschschule Aachen 1979 Atomindex INIS-mf-8266. 104 B. E. Gordon W. R. Erwin R. M. Lemmon and G. T. Peng fnt. J. Appl. Radiat. fsot. 1982 33 715. 105 J. S. Favier J. Wallaart and F. M. Kaspersen J. Labelled Comp. Radiopharrn. 1982 19 1125. lo' R. A. Houghton Life Sci. 1982 31 1805. I07 G. Toth M. Szuecs S. Benyhe F. Sirokman and M. Kramer Radiochem. Radioanal. Lett. 1983,56,209. I on J. Filip and L. Bohacek Czechoslovak Patent 192239/B 1981. 109 J. Filip and L. Bohacek Czechoslovak Patent 1971 18/B 1982.110 D. W. Robertson and J. A. Katzenellenbogen J. Org. Chem. 1982,47 2387. M. Lischewski and G. Adam J. Labelled Compd. Radiopharm. 1982 19 1231. Radiochemistry 33 1 use of tritium labelled borohydride as a reducing agent.'12 The location of tritium in compounds produced by a variety of the above techniques has been studied using tritium N.M.R.' l3 C.-Most current interest in the production of carbon-labelled compounds centres upon "C rather than I4C; the short half-life of "C often necessitates inovative chemistry to produce the desired product. Methods for optimizing the direct forma- tion of useful materials such as "CO '14 or nitrogen-containing "C c~mpounds"~ have been described. Reactions involving recoil "C atoms as a way of augmenting the number of carbon atoms in a molecular have been proposed,'16 although care must be taken in purifying the products because a mixture of labelled compounds usually results.Chromatography is of course useful for this purpose and h.p.1.c. has proved especially valuable for radiopharmaceutical production;' l7 the use of a capillary column has even allowed the isolation of ["Clmethane.' l8 Remote-control (e.g. for handling "CO "C02 and H'1CN)1'9 and automatic methods for the preparation of ''C-labelled compounds'20 are being rapidly developed in many laboratories e.g. 2-deoxy-~-glucose,'~' glucose,123 anti- 3-[I 'C]methyl-~-glucose,'~~ methyl iodide,'25 L-[S-methyl-''C]methi~nine.'~~ ~yrine,'~~ Most routes to "C-labelled molecules start from simple compounds such as ["Clcarbon dioxide from which labelled butanol,'26 pr~pandiol,'~' pal mi ti^'^^^'^^ and other carboxylic acids,'29 acetate anion,'30 and glucose'23 can then be produced.Methods to maximize the initial "C02 prod~ction'~~ as well as a study of its reaction in a micro-wave discharge'32 and its reactions with metallo-aldimines to make imino acids'33 (and so to ["C]ketoacids) have been described. I I2 B. Steiner K. J. Clemetson and E. F. Luescher Thromb. Res. 1983 29 43. 113 Y. S. Tang Ph.D Thesis University of Surrey Guildford U.K. 1982. I14 S. C. Jones G. D. Robinson A. Alavi E. Mclntyre and M. Reivich ref:85 p. 1352. 'I5 K. Roessler B. Lattke C. Mathias L. M.Al-Shukri and M. Vogt ref. 85 p. 1618. I16 G. Gundlach E.L. Sattler U. Wagenbach and K. Wittig ref 85 p. 1371. I I7 G. Berget M. Maziire J. M. Godot J. Sastre C. Prenant and D. Comar 'Preparation of "C-Labelled radiopharmaceuticals by the use of HPLC method' (CEA-CONF-66 18) Centre &Etudes Nucleaires de Saclay. 91 Gif-sur-Yvette France 1982. I18 G. Berger C. Prenant J. Sastre and D. Comar ref 85 p. 1486. I19 G.-J. Meyer T. Harms and H. Hundeshagen reJ 85 p. 1362. 120 M. J. Welch C. S. Dence and M. R. Kilbourn ref:85 p-1382. I21 S. A. Stone-Elander E. Ehrin and J. L.G. Nilsson ref 85 p. 1372. I22 P. Laufer and G. Kloster Int. J. App. Radiat. Isot. 1982 33 775. 123 K. Ishiwata M. Monma R. Iwata and T. Ido ref:85 p. 1347. I24 (a) D. van Haven P. de Clerq T. Vandewalle and C. Vandecasteeie Int.1. AppL Radiat. Isot. 1982 33 751; (6) D. van Haven P. de Clerq T. Vandewalle and C. Vandecasteele in 'AOC 3rd World Congress of Nuclear Medicine and Biology' ed. C. Raynaud Pergamon 1982 Volume 1 p. 1108. 12' J. Davis Y. Yano J. Cahoon and T. F. Budinger Int. J. AppL Radiat. Isot. 1982 33 363. lZ6 (a) F. Oberdorfer F. Helus W. Maier-Borst and D. J. Silvester Radiochem Radioanal. Lett. 1982 53 237; (b) F. Helus W. Maier-Borst F. Oberdorfer and D. J. Silvester ref. 85 p. 1501. 127 G. Berger M. Maziire C. Prenant J. Sastre A. Syrota D. Comar J. Radioanal. Chem 1982 74 301. 128 H. C. Padgett G. D. Robinson and J. R. Bamo Int. J. AppL Radiation Isot. 1982 33 1471. 129 B. Schmall P. S. Conti B. Sundoro-Wu J. R. Dahl J. K. Jacobsen and R. Lee 1.Labelled Comp. Radiopharm. 1982 19 1278. I30 V. W. Pike M. N. Eakins R. M. Allan and A. P.Selwyn Znt. J. Appl. Radiat. Isot. 1982 33 505. 131 T. Vandewalle and C. Vandecasteele ref:85 p. 1376. I32 K. Niisawa J. Saito K. Taki T. Karasawa and T. Nozaki re$ 85 p. 1616. 'I' (a) M. R. Kilbourn and M. J. Welch Int. J. Appl. Radiat. Isot. 1982 33 359; (b) M. R. Kilbourn and M. J. Welch ref 85 p. 1273. 332 D. S. Urch ["CIMethyl iodide'25 is a particularly useful reagent for introducing the "C-label at a known and usual stable site in a e.g. methiodide quinuclidinyl ben~ilate,'~' L-methionine 13' N-alkyl derivatives of 2-amino-6,7-dihydroxy- 1,2,3,4- tetrahydr~napthalene,'~'and anti~yrine.'~~ Other starting materials have included [''Cjphosgene { 1,3-bis(2-chloroethyl)nitrosourea,138 [2-''C]-5,5-dimethylox-a~olidine-2,4-dionel~~*'~} and [''Clformaldehyde (erthromycin A'41).Recent advances in l4C-labe1ling have included a rapid and efficient synthesis of [1,2-'4C]acetic the production of a series of 3-substituted in dole^,'^^ the use of an enzyme to make ['4C]ATP'44 and the description of a method for labelling bacteria with [14C]palmitic Nu~leotides'~'and a series of uridine deriva- tive~~~~ have also been labelled with 14C. 13N,'50.-A method for the synthesis of 13NH3 from 13C enriched targets using micro-wave radiation has been described.'48 13NH3 [from l60(p a)13N] has been used for the production of ~-['~N]glutamate,'~~ nitrous oxide can be made labelled either with 13N15* (pyrolysis of ammonium [13N]nitrate) or with H2150 has also been made."4 '*F.-Trying to produce 18F in a conventional thermal neutron reactor is rather like trying to run up a scree slope-you have to run hard and you don't get very far.Even so it has been tried'52 using the reactions 'Li (~,LY)~H followed by 160(3H,n)'8F in lithium hydroxide. The overall yields of 18F were about 40mCi. Considerable effort has recently been expended in attempting to design suitable mixtures in which nuclear reactions that produce "F can take place so that subsequent chemical reaction will deliver 18F in a convenient chemical form. If the deutron-neutron reaction takes place in a copper or tungsten vessel the 18F that adheres to the walls can be removed by heating in a hydrogen-helium mixture to give anhydrous Hl8F.lS3 Inconel-600 has also been studied as a container material,'54 but using neon-134 H.Svaerd K.Naagren P. Malmborg D. Sohn S. Sjoeberg and B. Laangstroem ref 85 p. 1519. 135 M. Maziire G.Berger J.-M. Godot C. Prenant J. Sastre and D. Comar J. Radioanal. Chem. 1983 76 305. 136 G.-J. Meyer A. Osterholz and H. Hundeshagen ref:85 p. 1286. 137 J. F. van der Werf H. D. Beerling-Van der Molen A. M. J. Paans T. Wiegman J. Korf and W. Vaalburg ref 85 p. 1296. 138 M. Diksic S. Farrokhzad S. Yamamoto and W. Feindel J. Nucl. Med. 1982 23 895. I39 J. Z. Ginos R. S.Tilbury M. T. Haber and D. A. Rottenberg J. Nucl. Med. 1982 23 255. 140 M. Berridge D. Comar D. Roeda and A. Syrota Int.J. Appl. Radiat. Isot. 1982 33 647. l4I A. J. Palmer V. W. Pike P. L. Horlock L. A. Perun L. A. Frieberg D. A. Dunnigan and R. Liss ref 85 p. 1275. 142 T. Elbert and J. Filip Radiochem. Radioanal Lett. 1983 57 21 1. 143 J. Schallenberg and E. Meyer 2.Naturforsch. Teil B 1983 38 108. 144 Z. Nejedly H. Tauchmanova J. Filip and J. Kolina Radiochem Radioanal. Lett. 1982 53 329. 145 S. Abaas FEMS Microbial. Lett. 1983 18 283. I46 V. Svoboda I. Kleinmann and J. Kolina Radioisotopy 1982 23 301. 147 J. L. Ruth S. K. White and D. E.Bergstrom J. Labelled Comp. Radiopharm. 1982 19 861. 148 R. A. Ferrieri D. J. Schlyer A. P. Wolf and B. Wieland ref 85 p. 1614. I49 K.Suzuki K.Tamate T. Nakayama T. Yamazaki Y.Kasida K.Fukushi Y. Muruyama H. Maekawa and H.Nakaoka ref 85 p. 1374. Is' G. Del Fiore J. M. Peters L. Quaglia N. Bougharouat D. Lamotte and T. Niethammer J. Biophys. Med. Nucl. 1982 6 163. 151 C. Crouzel and J. C. Baron ref 85 p. 1612. I s2 S. J. Gatley and W. J. Shaughnessy 1nt. J. Appl. Radiat. Isot. 1982 33 1325. I53 J. R. Dahl R. Lee R. E. Bigler B. Schmall and J. E. Aber Int. J. Appl. Radiat. Isot. 1983 34 693. J. C. Clark and F.Obderdorfer ref 85 p. 1337. Radiochemistry 333 hydrogen mixtures as the target gas. H18F can be used to make 18F-difluorine gas,155 to fluorinate aromatic system^"^ (via triazeno method) and to prepare 2-[18F]-2-deoxy-~-glucose'~~ (this compound can also be prepared starting with 18F. F'58 see ref 114). If the mixture CF,,H2 Ne is irradiated with deutrons a very reproducible yield of H18F is produced.159 The methods all produce F2 or HF in an anhydrous and carrier-free form.Water can however act as a useful target material if an 3He ion beam is available 160(3He,p)'8F. This reaction has been the basis of a series of successful radiopharmaceutical syntheses by the Julich group e.g. fluoroacetyl urokinase,160 6-['8F]-nicotininic acid dieth~lamide'~'-'~~ and 3-[IBF]-3-deoxy-~- glucose.'64 If the nuclear reaction takes place in a solution of ammonium acetate then acetyl [18F]hypofluorate is produced which can be used to make 5-[18F]-5-de~xyuridine'~~ This latter compound has also and 2-[18F]-2-deoxy-~-glucose.'66 using xenon [18]difl~oride169 been produ~ed'~~*'~~ to introduce the radioactive fluorine atom.Silver ['8F]fluoride continues to be used to produce labelled organic molecules e.g. alkyl fluorides,'70 6- or 2-['8F]-9-benzylpurine'71and 6-fluoromethyl- 19-norcholesterol.'72 Attempts to improve the fluoro-labelling of have included the use of crown ether fluoride reagent^."^ 35S,36C1.-Methods 17'35S-labelled thiosemicarbazone offor the preparation 2,4-dithiobi~ret,'~~ and also 36C1-labelled hypo- and an anticoagulant p~lyelectrolyte,'~~ chlorous acid and C102179 have been described. 67 Ga.-Desferrioxamine forms a stable complex with gallium (67Ga)180-'82 which can couple with human serum albumen thus providing a label. Other labelled gallium 155 M. G. Straatmann D. J. Schlyer and J. Chasko ref. 85 p. 1373. IS6 M.R. Kilbourn H. Saji and M. J. Welch ref. 124(b) p. 1101. I57 S. Levy D. R. Elmaleh and E. Livni 1. Nucl. Med. 1982 23 918. R. Iwata T. Takahashi M. Shinohara and T. Ido ref 85 p. 1350. I59 R. A. Ferrieri R. R. MacGregor S. Rosenthal D. J. Schlyer J. S. Fowler and A. P. Wolf ref:85 p. 1620. 160 C. N. Mueller-Platz G. Kloster G. Stoecklin and G. Legler re$ 85 p. 1645. 161 E. J. Knust H.-J Machulla and M. Molls ref. 85 p. 1643. I62 E. J. Knust C. Mueller-Platz and M. Schueller J. Radioanal. Chem. 1982 74 283. I63 E. J. Knust H.-J. Machulla and Ch. Astfalk Radiochem. Radioanal. Lett. 1983 55 249. E. J. Knust H.-J. Machulla and K. Dutschka Radiochem. Radioanal. Lett. 1982 55 21. I65 C.-Y. Shiue A. R.Wolf and M. Friedkin. ref 85. p. 1395.I66 C.-Y. Shiue P. A. Salvadori A. P. Wolf J. S. Fowler and R. R. MacGregor J. Nucl. Med. 1982,23 899. I67 S. Sood G. Firnau and E. S. Garnett Int. J. Appl. Radiat. Isot. 1983 34 743. I68 J. S. Fowler C. Y. Shiue A. P. Wolf P. A. Salvadori and R. R. MacGregor ref. 85 p. 1634. 169 G. Firnau R. Chirakal G. Schrobilgen and E. S. Garnett re$ 85 p. 1342. 170 M. Yagi Y.Murano and G. Izawa Int. E Appl. Radiar. Isot. 1982 33 1335. 171 T. Irie K. Fukushi 0. Inoue T. Yamasaki T. Ido and T. Nozaki Int. J. Appl. Radiat. Isot. 1982 33 633. I72 T. Kobayashi M. Maeda and M. Kojima ref 85 p. 1507. 173 L. A. Spitznagle C. A. Marino and S. Kasina ref 156 p. 636. 174 J. S. Ng J. A. Katzenellenbogen and M. R. Kilbourn J. Org. Chem. 1981,46 2520.175 T. Irie K. Fukushi T. Ido Y.Kasida and T. Nozaki hr. J. Appl. Radiat. hot. 1982 33 1449. 176 H. Renault Ann. Pharm. Fr. 1982,40 377. 177 W. R. Porter K. D. Williams and R. E. Peterson J. Labelled Compd. Radiopharm. 1982 19 881. 178 L. C. Sederel L. Van der Does A. Bantjes and Z. Kolar J. Labelled Comp. Radiopharm. 1982.19 1251. 179 H. A. Ghanbari W. B. Wheeler and J. R. Kirk in 'Proc. 4th Conf. on Water Chlorination; environmental impact and health effects' ed. R. L. Jolley W. A. Brungs J. A. Cotruvo R. B. Cummings J. S. Mattice and V. A. Jacobs Ann Arbor Sci. Pubs. Ann Arbor Mich U.S.A. 1983 volume 4 p. 543. I80 G. A. Janoki J. F. Harwig and W. Wolf ref. 85 p. 1405. I81 Y. Yokoyama Y. Ohmomo K. Horiuchi H. Saji H. Tanaka K. Yamamoto Y.Ishii and K. Torizuka J. Nucl. Med. 1982 23 909. I** A. G. Janoki J. F. Harwig and W. Wolf ref. 156 p. 689. 334 D. S. Urch compounds that have been prepared recently include the tri~atecholamide'~~ and the tetrasulphothalocyanine complex.'84 75 As,75Se.-The use of [76As]dimethylchloroarsineas an intermediate in the produc- tion of radiopharmaceuticals such as dimethylarsinopenicillamine has been de~cribed.'~~ Sodium hydrogen selenide (NaH7%e) which can be made by reducing [75Se]selenious acid with sodium borohydride can similarly be used as an inter- mediate to introduce selenium radioactivity into molecules such as fatty acids steroids etc.186*187 Br.-A variety of different techniques has been described (and the limitations reviewed188) for inducing s~dium[~~Br]bromide to react with organic molecules (i) with an alcohol in acetonitride solution with chl~rotrimethylsilane,'~~ (ii) with an alcohol carbon tetrachloride and triphenylpho~phine,'~' (iii) with estrone diol diacetate hydrogen peroxide and acetic acid.19' Organoboranes also react with sodium bromide (in the presence of chloramine-T) to produce the corresponding alkyl or aryl bromide (this work was done with 82Br).192 Labelled dibromine itself can be used in chloroform as in the formation of [6-82Br]cholestrol from 6-chloromer- cury chole~trol.'~~ The radiobromination of aromatic systems has been studied in the absence of and a range of other bromine-labelled molecules has been prepared triflu~robromomethane,'~~'~~ 4-bromomisonidazole,198 bromo-D-glucose ana-logue~,~~~ bromobenzodiazepine,200 bromo-estrogens201 etc.Tc.-The chemistry of technetium has been the subject of a general review,202 some v,'" electrochemi~try,~~~ particular reviews (valencies I-Iv,~'~ X-ray photoelectron I83 S. M. Moerlein D. D. Dischino K. Raymond F. L. Weitl and M. J. Welch re5 85 p. 1421. 184 J. E. van Lier and J. Rousseau ref 85 p. 1467. Ins F. Hosain A. Emran R. P. Spencer and K. S. Clampitt Int. J. Appl. Radiat. Isot. 1982 33 1477. I86 S. A. Sadek G. P. Basmadjian and R. D. Ice NucL Med. Commun. 1982 3 247. G. P. Basmadjian S. Sadek and R. D. Ice ref 85 p. 1482. inn K. D. McElvany M. J. Welch J. A. Katzenellenbogen S. G. Senderoff. G. E. Bentley and P. M. Grant Int.1.AppL Radiation Isot. 1981 32 41 1. 189 M. R. Kilbourn K. D. McElvany and M. J. Welch Int. J. Appl. Radiation Isot. 1982 33 391. 190 M. R. Kilbourn and M.J. Welch Int. J. Appl. Radiation hot. 1982 33 1479. 191 S. G. Senderoff K. E. Carlson D. F. Heiman J. A. Katzenellenbogen K. D. McElvany and M. J. Welch Int. J. Appl. Radiation Isot. 1982 33 545. 192 G. W. Kabalka K. A. R. Sastry and P. G. Pagni J. Radioanal. Chem. 1982 74 315. I93 L. Bo-Li J. Yu-Tai P.Zhong-Yun and M. Kojima J. Labelled Compd. Radiopharm. 1982 19 1089. I94 R. S. Coleman R. H. Seevers and A. M. Friedman 1.Chem. SOC.,Chem Commun. 1982 1276. 19s G. S. Petzold Dissertation Institute for Nuclear Chemistry Cologne University Cologne BRD 1982. 1% D. de Jong and B.W. van Haltern Int. J. AppL Radiat. Isot. 1982 33 387. I97 A. G. Rodriguez T. P. Estrada and G. V.Perez 4th Symposium on Nuclear- Radio- and Radiation- Chemistry Universidad Nacional Autonoma de Mexico (Centro de Extudios Nucleares) Mexico City Mexico 1982. I98 J. S. Rasey S. Freauff and K. A. Krohn J. Radiat. Res. 1982 91 542. I99 G. Kloster P. Laufer W. Wutz and G. Stoecklin reJ 85 p. 1626. 200 H.Scholl P. Laufer G. Kloster G. Stoeckiin ref 85 p. 1294. 20I S. W. Landvatter M. K. Mao J. A. Katzenellenbogen M. D. McElvany and M. J. Welch ref:85,p. 1292. 202 K. Schwochau Radiochem. Acta 1983 32 139. 203 A. G. Jones and A. Davison Int. J. AppL Radiat. Isotop. 1982 33 867. 204 A. Davison and A. G. Jones Int. J. Appl. Radiat. Isotop.1982 33 875. 2os C. D. Russell Int. J. Appl. Radiat. Isotop. 1982 33 883. Radiochemistry 335 spectroscopy,206 n.m.r.207) and of two new Gmelin supplement^.^^^*^^^ Recent pro- gress in the field of 99mTc-radiopharmaceuticalshas also been briefly reviewed?l0 as has the relationship between structure and2I1 activity for these compounds. The development of suitable 99mT~ 'generators' from which the isotope can be eluted as and when required continues to be of interest,212 as does the radiochemical purity of what actually comes off the The quality and stability2'" of technetium complexes has also been considered. Whilst the number of 'labelled complexes' of technetium is large and continues to expand rapidly it has to be admitted that quite often the exact chemical nature of what is formed is not well characterized -either as to structure composition or even valence state of the technetium.This is because most preparations start with Tc04-(VII) which is reduced in situ with Sn2+. A detailed study of products formed in citric acid however revealed217 oxo(bis-citrato)technatecomplexes with TcV or Tc'" (as hydroxo-etc.) depending upon the extent of reduction. Similarly reduction in the presence of aminopolycarboxylic acids gave complexes of Tc'" or Tc"' depending upon the PH.~'' The problem has been considered more generally for a range of ligands such as mercaptoethylamine pyr~phosphate,~~~ etc. The role of solvent and possible proton sources have also been investigated.220 A detailed study of iminodiacetate-technetium complexes revealed that many pharmaceutical prepar- ations are in fact mixtures.221 Other technetium compounds and complexes (mix- tures?) that have been reported recently have ligands such as cyclamen,222 ethylen- diamine,223 tr~polone,~~~ nitrogen heterocycles,225 substituted iminodiacetic acids,226 dithiocarbamate~,~~' and penicillamine.228 Univalent technetium can apparently be stabilized by r-acceptor ligands such as i~ocyanide.~~~ 206 V.N. Gerasimov S. V. Kryuchkov A. F. Kuzina V. M. Kulakov S. V. Pirozhkov and V. I. Spitsyn Dokl. Akad. Nauk SSR 1982 266 148. 207 K. J. Franklin C. J. Lock B. G. Sayer and G. J. Schrobilgen J. Am. Chem. Soc. 1982 104 5303. '208 'Technetium. Suppl. Vol. 1 General Properties Isotopes Production Biology' ed.H. K. Kupler and C. Keller Gmelin Handbook of Inorganic Chemistry Springer Berlin BRD 1982. 209 'Technetium. Suppl. Vol. 2 Metal-Alloys-Compounds-Chemistry in Solution' ed. G. de Alleluia J. Burgess R. D. Peacock C. Keller S. Moebius S. Ruprecht and K. Schwochau Gmelin Handbook of Inorganic Chemistry Springer Berlin BRD 1982. 210 B. A. Johannsen and B. Johannsen Drsch. Gesundheitsw. 1982 37 1753. 21 I R. Muenze re$ 85 p. 1453. 212 S. M.Milenkovic J. L. Vucina L. M.Jacimovic E. S. Karanfilov and T. V. Memedovic Isotopenpraxis 1983 19 85. 213 P. Naesman and T. Vaeyrynen Eur. J. Nucl. Med, 1983 8 26. 214 J. Cifka Int. J. Appl. Radiat. isot. 1982 33 849. 215 V. Jananovic T. Maksin and J. Bzenic Eur. 1.Nucl.Med. 1983 8 179. 216 R. Berger Int. J. Appl. Radiat. Isot. 1982 33 1341. 217 R. Muenze I. Hoffmann R. Dreyer and I. Dreyer J. Radioanal. Chem. 1982 74 63. 218 S. Seifert B. NOH and R. Muenze Int. J. Appl. Radiat. Isot. 1982 33 1393. 219 M. A. Gracheva 0. N. Ilyushchenko G. E. Kodina and V. I. Levin ref 85 p. 1535. 220 J. B. Slater J. F. Harwig and W. Wolf re$ 85 p. 1605. 22 1 C. D. Russell and A. G. Speiser Int. J. Appl. Radiat. Isot. 1982 33 903. 222 D. E. Troutner W. A. Volkert C. Reid T. Hoffman and R. A. Holmes ref 85 p. 1600. 223 W. A. Volkert D. E. Troutner and R. A. Holmes Int. J. Appl. Radiat. Isot. 1982 33 891. 224 L. A. Spitznagle C. A. Marino and S. Kasina J. Radioanal. Chem 1982 74 307. 225 S. Seifert R. Muenze and B.Johannsen Radiochem. Radioanal. Lett. 1982 54 153. 226 A. E. A. Mitta C. Archiprete and E. G. Gros J. Labelled Cornp. Radiopharm 1982 19 1602. 227 J. Baldas and P. M. Pojer in 'Annual Review Research Projects 1981' ed. D. W.Keam (ARL/TR-050) Australian Radiation Laboratory Melbourne Australia 1983 p. 77. 228 A. Yokoyama and K. Horiuchi Int. J. Appl. Radiat. Isot. 1982 33 929. 229 A. G. Jones A. Davison M. J. Abrams et al. ref 85 p. 1594. 336 D. S. Urch Pd In.-The preparation has been described of 109Pd-8-hydroxyquinidine as well as 109Pd-labelled porphyrin~.~~' In-tetraphenylp~rphyrin~~' has also been made and the relative efficiency of all those compounds for labelling lymphocytes and platelets compared. The only other recently reported work with indium concerns the 'labelling' of high molecular weight proteins using either 12' In-~xine~~~ or I 13"In bound to tran~ferrin~~~ in the presence of chelating groups based on iminodiacetic or nitrilotriacetic acids.Te.-The synthesis of 34123mTe]nonadecanoic and 18-methyl- 17-['23Te]nonadec-9-enoic acids for use as heart imaging agents has been described.234 Carrier-free ItsmTe in the tetravalent state in brine forms a 1.-Most recent work concerning the preparation of compounds labelled with radioactive iodine has centred upon the incorporation of 1231 or I2'I although some materials with I3'I have been reported. A lot of activity has upon a-substituted long chain fatty acids where the end of the chain substituent is either iodine or an iodine-containing group.Exchange reactions between 16-iodohexadec- 9-enoic or 17-bromoheptadecanoic and radioactive sodium iodide in acetone (or a higher ketone) procede at temperatures of about 100°C and are facilitated by ultrasonic irradiation. The preparation of 15( p-iodopheny1)pen- tadecanoic acid was brought about using an organic thallium intermediate,240 but the same product can be made by a simple exchange reaction.241 Similar acids but with a methyl side chain e.g. 14- or 15-(p-[1231]iodophenyl),2-or 3-(R,S)-methyl (tetra- or penta)-decanoic acid have also been labelled242 with radioactive iodine. Tellurated substituted fatty acids 15-( p-['251]iodophenyl)-6-tellurapentadecanoic acid have been made as well.243*244 The rather more complex [1231]iodohistamine- labelled A3-tetrahydrocannabinol-1 1 -oic acid has been prepared.245 A very wide range of other compounds usually with biochemical tracer potential has also been made; 1,2-diphenyl-3,3-dichlorocyclopropane246 (radioactive iodine is found to replace chlorine most effectively when the thallium 'iodine carrier' or triazine hydrolysis methods are used) iodinated I-substituted 4-~henylpiperazines,~~~ 230 S.C. Srivastava R. A. Fawaz T. R.T. Wang T. Prach P. Richards and P. 0.Alderson ref:85 p. 1392. 23 I C. Cloutour J.-C. Pommier D. Ducassou and L. Vuillemin fnt. J. Radiat. hot. 1982 33 1311. 232 B. J. Weiblen A. J. Melarango N. Catsimpoolas and C. R.Valeri J. Immunol. Methods 1983 58 73. 23.3 A. Rokos B. Angelis and J.Cifia Radioisotopy 1981 22,649. 234 G. P. Basmadjian R. D. Ice and S. L. Mills Nucl. Med. Commun. 1982 3 150. 235 Y. Maruyama and Y. Nagaoka Radiochem. Radioanal. Lett. 1983 56 23 1. G. El-Shaboury and M. El-Garhy ref 85 p. 1529. 236 237 F. Riche M. Vidal J. P. Mathieu G. Busquet M. Comet S. Coornaert A. Bardy and J. Godart ref 85 p. 1321. 238 F. Riche M. Vidal J. P. Mathieu M. Comet S. Coornaert and M. L. Conti Radiochem. Radioanal. Lett. 1982 53,225. 239 W. Vanryckeghem A. Bossuyt R. van den Driessche J. Mertens and P. van den Winkel J. Biophys. Med. Nucl. 1982 6 159. 240 P. V. Kulkarni and R. W. Parkey ref 85 p. 1319. 24' M. Eisenhut Int. J. Appl. Radiat. Isot. 1982 33,499. 242 M. M. Goodman G. Kirsch and F. F.Knapp ref:85 p. 1316. 243 M. M.Goodman F. F. Knapp A. P.Callahan and L. A. Ferren J. Nuel. Med. 1982 23,904. 244 F.F.Knapp M. M. Goodman and A. P.Callahan ref 85 p. 1323. 245 B. Law P. A. Mason A. C. Moffat and L. J. King J. Labelled Comp. Radiopharm. 1982 19 915. 246 G. P. Basmadjian D. L. Gilliland R. A. Magarian R. D. Ice and A. P. Marchand ref 85 p. 1484 247 (a) R. N. Hanson ref 85 p. 1303; (b) R.N. Hanson fnt. 1.Appl. Radiat. Isot. 1982 33,629. Radiochemistry 337 Jiod~estradiol,~~~ ['231]iodoamphetamine,248 16~u-['~~I 3,3',5 tri-['251]iodo-thyr~nine,~~~.~~' as substituted guanidines,2s2 ~ytidines,~'~ as well ~racils,~~~ and even humic Toluidine Rose Be~~gal,~~~ ~radines,~~~ a derivative of vitamin B1 (cyanocobalamin-d -['2sI]iodohistamide),2s9 and an insulin frag- ment260 have also been labelled with radioactive iodine.ortho-Iodohippuric acid has been prepared in a variety of ways either by exchange with Na'3'126' or by exchange with 1231produced by the irradiation of 124Te02 with protons or '22Te02 with deutrons.262 The relative merits of various radio-iodination procedures for aromatic compounds have been considered.263 Heavier Elements.-Ytterbium- 169 has been incorporated into a phytate complex264 for use in nuclear medicine. Osmium-191 ('910sC14 in HC1) can be exchanged for the iron in ferrocene in 45% yield to give radioactive osmocene.26s Radioactive versions of platinum-containing anti-cancer drugs containing '9smPt have been pre~ared~~~,~~' At.-Studies of the chemistry of astatine have permitted the boiling points of At1 and elemental astatine to be estimated268 (486 and 503 K respectively).Complex ions of the type AtX2- (X = C1 Br I,269 SCN or CN270) have also been investigated. It has been found that astatine in hot dilute acid solution undergoes a substitution reaction with benzene to form a~tatobenzene.~~' The only other aspect of astatine chemistry to be reported recently is the synthesis of the anti-tumour drug 6-[" Atlastato-2-methyl-1,4 naphthoquinol as the bis-diphosphate salt.272 248 R. M. Baldwin T. H. Lin and J. L. Wu ref 85 p. 1305. 249 F. Therain J. Gros and A. Souchu J. Biophys. Med. Nucl. 1982 6 155. 250 M. B. Espejel and C. J. Lezama ref 197 p. 23. 25 I R. Somack S. K. Nordeen J.W. Apriletti J. D. Baxter and N. L. Eberhardt Endocrinology 1982 111 1758. 252 P. Angleberger M.Wagner-Loeffler and R. Hruby ref 85 p. 1479. 253 U. Linz J. Labelled Comp. Radiopharm. 1982 19 1151. 254 J. R. Mercer L. I. Wiebe E. E. Knaus W. Maier-Borst and F. Helius ref 85 p. 1398. 255 A. Freud D. Solenchek E. Ben-Hur and 2.Teitelbaum in 'Research Laboratories Annual Report-1981' (1 A- 1379 Israel Atomic Energy Commission Tel Aviv Israel 1982 188. 256 J. C. Lobartini N. R. Curvetto and G. A. Orioli Int. J. Appl. Radiat. Isot. 1982 33 1331. 257 S. Soenarjo Majafah BATAN 1981 14 1. 258 E. G. Alekseev and V. M.Zaitsev J. RadioanaL Chem. 1983 78 53. 259 T. M. Hoults Clin. Chim. Acta. 1982 126 315. 260 Y. M. Megahed M. F. Abdel-Wahab M.A. Zewall and A. M. Shalaby Isotopenpraxis 1983 19 274. 26 I K. Kopicka P. Hradilek and L.Kronrad Jad. Energ. 1982 28 369. 262 G. J. Beyer G. Pimental L. Kronrad and P. Hradilek ref 85 p. 1488. 263 H. Youfeng H. H. Coenen G. Petzold and G. Stoecklin J. Labelled Comp. Radiopharm. 1982 19,807. 264 N. H. Agha A. M. Al-Hilli H. A. Hassen M. H. S. Al-Hissoni and K. M.Miran Int. J. Appl. Radiat. Isot. 1982 33,673. 265 G. Schachschneider and M. Wenzel J. Labelled Comp. Radiopharrn. 1982 19 1071. 266 W. Cole J. Wiza B. Odenheirner. W. Wolf J. D. Hoeschele T. A. Butler and R. D. Srnyth ref:85 p. 1400. 267 J. D. Hoeschele T. A. Butler J. A. Roberts and C. E. Guyer Radiochim. Acra. 1982 31 27. 268 K. Otozai and N. Takahashi Radiochim.Acta 1982 31 201. 269 R. Dreyer I. Dreyer F. Roesch and G.-J. Beyer Radiochern. Radioanal. Letf. 1982 54 165. 270 R. Dreyer I. Dreyer M. Pfeiffer and F. Roesch Radiochern. Radioanal. Lett. 1983 55,207. 27 1 (a) L.Vaslros Yu. V. Norseyev and V. A. Khalkin Dokl. Akad. Nauk SSSR 1982 266 120; (b) L. Vaslros Yu. V. Norseyev D. D. Nhan and V. A. Khalkin Radiochem. Radioanal. Lett. 1982 54 239. 272 (a) I. Brown Radiochern. Radioanal. Lett. 1982 53,343; (b) I. Brown ref 85 p. 1389. 338 D. S. Urch 4 Chemicals Effects of Nuclear Transformations Chemical reactions intitated by nuclear reactions and also nuclear decay processes but excluding radiation chemistry will be considered in this section of the report. All aspects of this subject are discussed in depth in the book ‘Modern Hot Atom Chemistry and its Applications’.273 The topic is discussed in Volume 3 of Majer’s ‘Foundations of Nuclear Chemistry’,’’ and recent progress was discussed at the eleventh hot atom chemistry symposium274 which was eventually held at Davis University in 1982.Szilard-Chalmers type reactions have been studied in to determine the effects the passage of high energy recoil particles have upon the exchange of ions between different sites as a function of energy. Tritium.-Detailed trajectory calculations have been reported for the system hot 3H + CH4;277 calculations for the hot 3H + CH3NH2 system have suggested278 the possibility of NH2 replacement by 3H via a Walden inversion route. Experimental studies with ethyl and 1,2-difl~oroethylene~~~ at various pressures have revealed the importance of vibrational excitation following the 3H for H labelling reaction.Such excitation was found to be even more important in the reactions of recoil tritium atoms with monogermane where neither H3H nor GeH33H yields were affected by the addition of scavanger or the amounts of added moderator.281 In the liquid phase reactions with chloromethanes282 and chl~roethylenes~~~ have been studied. Very low yields of H3H were found; indeed in carbon tetrachloride 99% of the recoil atoms did not react (to form a stable bond) whilst translationally excited. Not surprisingly labelled polymers were the major yield from the unsaturated molecules. In the solid state the reactions of recoil tritium atoms with ethane adsorbed on a zeolites have been investigated.284 Whilst the mass spectrum of propane shows C3H5+ to be the commonest ion the major products formed by the decay of a tritium atom in multi-tritiated propane in the presence of benzene or toluene were labelled n- and iso-propyl arene~.~~’ This result may be rationalized by assuming that whilst the initial ionization of propane yields C3H7+ the reaction C3H7+-* C3H5+ + H2 has a low activation energy and can proceed rapidly enough in a mass spectrometer for the ally1 ion to be formed extensively.11 C,I3N,”0.-The reactions of recoil 13N with methanol and [2H4]methanol have been studied286 and showed neither temperature nor isotope effects. “C and I3N 273 T. Tominaga and E.Tachikawa ‘Modern hot-atom chemistry and its applications’ Springer Berlin BRD 1981. 274 ‘Eleventh International Hot Atom Chemistry Symposium’ Abstracts ed. J. Root University of California at Davis California U.S.A. 1982. 275 P. A. Newell and L. V. C. Rees Zeolites 1983 3 28. 276 A. Dyer Q. Guan-Lin and L. V. C. Rees Zeolites 1983 3 108. 277 T. Valencich J. Chem. Phys. 1983 79 671. 278 R. S. Asatryan I. A. Abronin and A. N. Nesmeyanov Izv. Akad. Nauk SSR Ser. Khim. 1982 1958. 279 Y. Tang E. Wu J. W. Anderton and R. R. Clark J. Chem. Phys. 1983 79 2181. 280 E. E. Siefert D. D. Smith R. E. Tricca P. M. Ayoub and Y. N. Tang J. Am. Chem. SOC. 1983 105,330. 2n I M. Castiglioni and P. Volpe Polyhedron 1983 2 225. 282 J. R. Veenboer and G.A. Brinkman Radiochirn. Acta 1982 31 7. 283 J. R. Veenboer and G. A. Brinkman Radiochirn. Acta 1982 30 1983. 284 (a) T. V. Tsetskhladze N. Ya. Tsibakhashvili Khim. Vvs. Ehnerg. 1983 17 86; (6) V. A. Barnov and T. V. Tsetskhladze Radiokhimiya 1982 24 264. 285 F. Cacace R. Cipollini and P. Giacomello J. Phys. Chem. 1982 86 2062. 286 Y. Sensui K. Tomura and T. Matsuura Radiochem. Radioanal. Lett. 1982 55 39. Radiochemistry 339 reactions in solids have been reviewed287 and the importance of radiation dose in determining the distribution of products labelled with llC 13N,and 150has been emphasized.288 18 F.-The gas-phase chemistry of recoil fluorine has been reviewed289 and the reactions with liquid-phase halogenomethanes studied (CCl, CHC13 CFC13).290 Thermalized 18F atoms (using excess SF as bath gas) have also been investigated with hydrocarbons,291 and alkyl ~tannanes.~~~ "Si.-The reactions of recoil silicon atoms [31 P(n,pP1 Si] in phosphine trimethyl- silane mixtures have been shown to give rise to a range of labelled pr0ducts.2~~ In many cases the proposed reaction mechanisms are quite complex and involve the facile rearrangements of silylene intermediates.35S.-A most useful bibliography of recoil sulphur has a recently appeared,295 from Sofia University. C1.-The formation and reactions of vibrationally excited molecules produced as a result of a substitution reaction involving a recoil 'hot' atom have been discussed both in and in particular for systems such as chloromethyl cyclopropane chlorocyclobutane The interconversion of these two isomers was initiated by 38Cl for C1 substitution.Other recent work involving recoil chlorine has been in condensed phases. 5-Chlorourasil 5-chloro-2'-deoxyuridine,and 5-chlorouridine will all react298 with recoil ,'Cl in aqueous solutions to yield the labelled parent molecules as the major organic product (but in small absolute yield). In liquid CC14 CHC13 and CFCl, the reactions of 34mCl and 38Cl have been compared; cage and radical recombination reactions were identified.290 The reactions of recoil chlorine in liquid mixtures e.g. ethyl chloridezw or n-butyl chloride300 with hydrocarbons alcohols and aniline have been investigated and the results analysed by the theory of Kontis and Ur~h.~" Similar studies have been made with aromatic molecules chlor~toluenes,~~~ and halogenoaniline~.~~ o-dichlor~benzene,~~~ The effect of going to the solid state for such mixtures has also been rep~rted.~~*~~~ 287 K.Roessler M. Vogt A. Izquierdo C. Mathias and L. M. Al-Shukri in 'Keorn- Radio- Strahlenchemie- Grundlagen und Anwendungen' Karlsruhe Gesellschaft Deutscher Chemiker Frankfurt-am-Main BRD 1982. 288 G. A. Brinkman Int. J. Appl. Radiat. Zsot. 1982 33 525. 289 J. W. Root Adu. Chem. Ser. (No. 197) 1981 p. 80. 290 G. A. Brinkman and J. Visser Radiochem Radioanal Lett. 1982,54 331. 29 1 J. W. Root C. A. Mathis R Gurvis K.D. Knierim and S. H. Mo Adu. Chem. Ser. (No.197) 1981 p. 207. 292 M.van der Ley B. W. van Halteren and G. A. Brinkman Radiochem. Radioanal. Len 1983 57 55. 293 M. Kikuchi J. A. Cramer R. S. Iyer J. P. Frank and F. S. Rowland J. Phys. Chem 1982 86 2677. 294 S. H. Mo,J. D. Holten (III) S. Konienny E. C. Ma and P. P. Gaspar J. Am Chem. SOC.,1982,104,1424. 295 D. Todorovski and D. P. Koleva 'Hot Atom Chemistry of Sulphur' Khimicheski Fakultet Sofia University Sofia Bulgaria 1982. 296 L. D. Spicer Adu. Chem Ser. (No. 197) 1981 p. 123. 297 L. J. Ferro PhD. Thesis Utah University Salt Lake City Utah U.S.A. 1982 (Microfilm order No. 82-20 778). 298 L. J. Arsenault A. J. Blotcky M. L. Firouzbakht and E. P. Rack Radiochim. Acta. 1982 31 171. 299 A. S. Agrawal and B. S. M. Rao Radiochim Acta 1982 31 13. 300 S.F. Patil R. N. Bhave and A. R. Galande Radiochern. Radioanal. Lett. 1983 57 151. 301 S. S. Kontis and D. S. Urch. Radiochim. Acta 1973 20 39. 302 R.N. Bhave B. S. M. Rao B. W. van Halteren and G. A. Brinkman Radiochim. Acta 1982 31 185. 303 R. N. Bhave and B. S. M. Rao Radiochim. Actq 1982 30,189. 304 V. D. Dedgaonkar S. Mitra and S. Waghmore Radiochem. Radioanal. Lett. 1983 56 87. 305 S. S. Gigoo A. S. Agrawal R. N. Bhave and B. S. M. Rao Radiochem. Radioanal. Left. 1982,53 195. 340 D. S. Urch First Row Transition Metals.-The reactions of recoil chromium atoms in solid and pentane solutions of chromium hexacarbonyl have been studied.306 In the solid state the thermal annealing of 51Cr1*1-doped ammonium dichromate was found307 to give similar results to the neutron irradiation of ammonium dichromate.Related experi- ments with permanganate [,,Mn(n y)56Mn] investigated308 the effects of isochronal heating on the distribution of manganese valency states. Solid state studies for a variety of cobalt systems have also been reported tri~(acetylacetonato),~~~ tri~(dipyridyl),~" and [Co(H,O),]. [Co EDTAI2. 4H20.3' I Br.-76Kr and 77Krdecay by electron capture (e.c.) and by p' (84%) + e.c. (l6%) respectively giving rise to bromines with low recoil energies and various charge states. The chemistry of these different 76Br and 77Br species in pr~pylene,~'~ perflu~ropropylene,~ethyl and trifluoromethyl halides3I4 has been l2 investigated in some detail. For the most part bromine substitution reactions were shown to have an efficiency of only a few per~ent.~" Neutron irradiation initiated reactions in aqueous solutions of bromo-nucleotide bases give small yields of labelled (80Br) parent molecules.298 Annealing studies of the fate of 80mBr in bromates (potassium316 and calcium317) have been made; the importance of surface states in understanding annealing behaviour has been empha~ized.~'~ In mixed crystals K20sBr,-K2SnC1 the recoil reaction of bromine initiated by both 81Br(n,y)82Br and 79Br(y 2n)77Br have been studied and compared.318 Second Row Transition Metals.-The chemistry of recoil Mo atoms in molybdenum hexacarbonyl has been investigated and labelled Mo(CO) was found when Fe(CO), MoCl mixtures were irradiated with neutrons.306 The disruptive effects within a molecule of p-decay p' decay electron capture and isomeric transition have been studied3I9 for oxymolybdenum phthalocyanine by comparing the effect of p-with that of the p' etc.decay of 90M~(t~ decay 99Mo(to99T~) 90Nb); bond rupture is least for p-decay. The effects of isomeric transition in a chemically bound atom have also been studied320 for 95mTCF62- (as potassium salt) both in the solid state where 90% retention was found and in solution where retentions of as low as 1% were found. Neutron irradiation of ruthenium( 11) A-tris( 1,lO-phenanthroline) per- chlorate solutions gave low yields (1-2%) of the parent molecule but less than 306 T. Muto and H. Ebihara Radiochim. Acta. 1982 31 179. 307 M. I. Stamouli Radiochim.Acta 1982 31 117. 308 V. G. Dedgaonkar S. Mitra and S. A. Kulkarni J. Univ. Poona Sci Technol. 1981 54 27. 309 Y. Sakai H. Nishioji S. Yamauchi and T. Tominaga Radiochem. Radioanal. Lett. 1982 53 215. 3 10 M. I. L. Maretti and'C. H. Collins Cienc. Cult. (Sao Paulo) Suppl. 1982 34 378. 31 I G. Albarran C. Archundia and A. G. Maddock Radiochim. Acta. 1982 30 199. 312 D. de Jong G. A. Brinkman B. W.van Halteren and J. Th. Veenboer Radiochem. Radioanal. Lerr. 1983 55 231. 313 D. de Jong G. A. Brinkman and B. W. van Halteren Radiochem. Radioanal. Let(. 1983 56 165. 3 I4 D. de Jong G. A. Brinkman and B. W. van Halteren Radiochem. Radioanal. Lett. 1982 55 113. 315 D. de Jong 'Proefschrift (Dr.) 'University of Amsterdam Netherlands 1982.3 I6 S. Fernandez-Valverdo M. Jirnenez-Reyes J. Serrano J. de la Torre and A. G. Maddock Radiochim. Acta 1982 31 19. 317 V. G. Dedgaonkar R. S. Lokhande and D. A. Bhagwat J. Univ. Poona Sci. Technol. 1981,54 37. 318 H. Mueller and P. Bekk '4th Symposium on Nuclear Chemistry Radiochemistry and Radiation Chemistry' Centro de Estudios Nucleares Universidad Nacional Autonoma de Mexico Mexico City 1982 p. 47. 319 K. Yoshihara H. Sugasawa and T. Sekine Radiochem. Radioanal. Left. 1983 56 349. 32U E. Ianovici 0.Lerch G. Zahner and A. G. Maddock Radiochim. Acta. 1982 31 79. Radiochemistry 341 of the enantiomeric compound,32' from which it may be concluded that most 'retention' probably results from the central ruthenium atom not being dislodged from the complex by the (n,y) reaction.1.-The chemistry of recoiling "'I species in iodo-aromatic compounds as solids and in solutions of benzene or methanol have been investigated322i323 to determine the roles of neutral and charged species. Recoil I2'I can give rise to labelled parent molecules when solutions of iodo-nucleotide bases are neutron irradiated.298 Heavier Elements.-The reactions of recoil thallium produced either by a-decay of or by the n,y reaction (to give 204Tl),325 "'Bi (to give 208Tl)324 in T113Tl'11 .C16 have been studied to determine the valence-state distribution of the radioactive thallium atoms. Annealing studies revealed that extensive isotope-exchange reactions take place in the solid state. Recoil astatine can also be produced either by electron capture326 or by radon decay,327 and its reactions with nitrobenzene chloronitroben- zene and chlorobenzene have been the object of detailed study.The chemical effect of a-decay has been studied for 235U bound in various complexes. The 'retention' that is observed depends greatly upon the solution pH which suggests that a-decay does indeed cause the uranium atom to break its chemical bonds and that the complex is reformed by finding free ligands in solution.328 5 Radiochemistry and Nuclear Power Sources of Uranium.-There is considerable research activity to determine ways in which uranium might be extracted from sea water using different possible adsor- bent~~~~ and ion-exchange resins.330 Aluminium phosphate33 * and a variety of materials based on hydrated titanium (e.g.with activated charc~al,~~~,~~~ with activated charcoal or made into granules with polyacrylic acid hydroxide as binder)335 have been shown to be quite efficient. So also was the tetraethyleneglycol dimethacrylate cross-linked poly(acry1amidoxime) resin.336 Nuclear Waste.-A very wide range of radioactive elements is produced by the operation of a nuclear reactor and a thorough knowledge of the chemistry and 32' K Sasaki N. Furukawa and H. Yamatera Radiochirn. Acta. 1982 31 121. "* M. Sharon and R. S. Birajdar J. Univ. Poona Sci. Technol. 1981 54 217. 323 M. Sharon and R. S. Birajdar J. Univ. Poona Sci. Technol. 1981 54 229. 3 24 S. Fernandez-Valverde G. Duplatre and J. M. Paulus Radiochirn.Acta. 1982 31 131. 325 S. Fernandez-Valverde 0.Lira de Vega and A. G. Maddock Radiochim. Radioanal. Lett. 1983,55 183. 326 L. Vasaros Yu. V. Norseyev and K. Berei Radiochim. Acta. 1982 31 75. 321 L. Vasaros Yu. V. Norseyev V. I. Forrninykh and V. A. Khalkin Radiokhirniya 1982 24 95. 328 S. I. I. Naqvi and P.Glentworth Palc J. Sci. fnd. Res. 1980 23 5. 329 Yu. A. Afanas'ev L. T. Azhipa A. I. Ryabinin N. B. Savenok and V. P. Eremin Radiokhirniya 1982 24 258. 330 K. Schwochau L. Astheimer H. J. Schenk and E. G. Witte 2. Naturforsch. Teil. E 1982 37 214. 33 I H. Seki I. Kashiki M. Sakai and A. Suzuki Hokkaido Daigaku Suisangakubu Kenkyu fho 1982,33,166. 332 N. Ogata Nippon Kaisui Gakkai-Shi 1982 35 266. 333 S. Shunsaku K. Sakane T. Hirotsu A.Fujii and T. Kitamura Nippon Kaisui Gakkai-Shi 1981,35 156. 334 S. Kotoh K. Sakane T. Hirotsu A. Fujii and T. Kitamura Shikoku Kogyo Gijutsu Shikenjo Hokuku 1981 13 121. 335 Y. Miyai S. Katoh and K. Sugasaka Nippon Kaisui Gakkai-Shi 1981 35 162. 336 K. Sakane T. Hirotsu N. Takagi S. Katoh K. Sugasaka Y. Umezawa N. Takai and H.Takahashi Nippon Kaisui Gakkai-Shi 1982 36 101. 342 D. S. Urch thermodynamic properties of complexes of these elements is required for the formu- lation of suitable separation and disposal techniques. The recent compilation of such data for the actinides is therefore to be welcomed.337 More specific work has shown that diphenyl(dialky1 carbamoylmethyl) phosphine may be used to extract transplutonium elements from acid solutions and that fission product radio- nuclides can be separated by adsorption on diethyleneglycol ~uccinate.~~~ Other recent work in this field has tended to be more element specific e.g.the use of activated-carbon filters for the removal of iodine iodides,340 c0balt-60,~~' and xenon,342 or a cryogenic process for krypton separation,343 or the use of molecular sieves to collect tritiated water vapour and oxides of or methods to remove I4CO2 from gas streams.344 The removal of ruthenium either by complex formation345or by adsorption346 has also been investigated. Nuclear Waste Disposal.-Nuclear waste may be disposed of either at sea or on land. And whilst in either case it is to be hoped that radioactive isotopes would be contained it is necessary to examine what their behaviour might be were they to escape.For this reason the fate of yttri~m-90~~~~~~~ in sea water and cerium- 144349,350 as well as niobium-95 cobalt-60 and chromium-51,3S' have been studied in detail. On land the current research into the adsorption of transurani~~~~" and fission b,c,d ions by clays and by igneous was reviewed at an International Symposium on 'The migration in the terrestial environment of long-lived radionu- clides from the nuclear fuel cycle'.352 Decontamination.-Reports have appeared describing decontamination procedures for problems as diverse as a hot tritium laboratory353 and a plutonium-contaminated 337 N. Edlestein J. Bucher R. Silva and H. Nitsche Report No. 14325 Lawrence Berkeley Lab.University of California USA. 1983. 338 M. K. Chmutova N. P.Nesterova N. E. Kochetkova 0.Eh. Kojro and B. F. Myasoedov Radiokhimiya 1982 24 31. 339 M. B. Hafez B. M. Abo El-Khair J. Radioanal. Chem. 1983 78 25. 340 J. G. Wilhelm 'Seminar on the testing and operation of off-gas cleaning systems at nuclear facilities' International Atomic Energy Agency (IAEA-SR-72) Vienna Austria 1983 p. 178. 34 1 R. Litman P. Jones and J. Ring Radiochem. Radioanal. Lett. 1982 54 359. 342 H. Ringel ref 340 p. 417. 343 R. von Ammon W. Bumiller E. Hutter G. Knittel C. Mas and G. Neffe ref 340 p. 41 1. 344 C. H. Cheh R. W. Glas and V. S. Chew ref 340 p. 471. 345 J. P. Glatz 'Kationische Ruthenium nitrosyl komplexe in radioaktiven Abfalloesungen' Dissertation (DSc) Saar University Saarbruecken B.R.D.1980. 346 'Control of semivolatile radionuclides in gaseous effluents at nuclear facilities' IAEA Tech. Report-No 220 International Atomic Energy Agency Vienna Austria 1982. 347 A. N. Nesmeyanov and A. A. Volkov Radiokhimiya 1982,24 247. 348 A. A. Volkov V. V. Anikeiv and A. A. Lobanov Radiokhimiya 1982 24 382. 349 A. N. Nesmeyanov L. S. Khova and A. A. Volkov Radiokhimiya 1982 24 386. 350 A. N. Nesmeyanov L. S. Khova A. A. Volkov and Yu. A. Sapozhnikov Radiokhimiya 1982 24 542. 351 L. S. Khova A. A. Volkov E. N. Shumilin and Yu. A. Sapozhnikov Vestn. Mosk. Univ. Ser. 2 Khim. 1982 23 306. 352 'International Symposium on migration in the terrestial environment of long-lived radionuclides from the nuclear fuel cycle' (Knoxville Tenn.U.S.A 1981) International Atomic Energy Agency Vienna Austria. 1982. (a) A. Billon ref 352 p. 167; (6) M. Y. Farah A. S. Abdel-Gawad N. Z. Misak W.E. Abdelmalik E. Mitry and H. B. Maghrawy ref 352 p. 70; (c) A. S. Abdel-Gawad N. 2. Misak N. B. Maghrawy and A. Shafik reJ352 p. 812; (d) L. Carlsen and P. Bo ref 352 p. 97; (e) K. Anderson B. Torstenfelt and B. Allard re$ 352 p. 11 1. 353 J. R. Harper and R. Garde Report LA-9056-MS Los Alamos National Laboratories 1981. Radiochemistry portion of Nevada.354 Rather more down to earth is a description of the use of high pressure freon for cleaning up mildly contaminated equipment355 and the use of painted surfaces to adsorb radionuclides from solutions.356 6 Miscellaneous The half-lives of 253Es (20.31 * 0.16 245Cm (8845 * 200 years),358 and "Rb[5.56 f0.025) x 10" years]359 as well as the decay constant for the spontaneous fission of 238U(6.6x lo-'' years-')360 have been determined recently whilst modest interest continues to be given to the changes in half-life that can be ascribed to chemical effects (51Cr).361 And finally for something quite different the chemistry of the light isotope of hydrogen muconium has been reviewed.362 354 355 356 357 358 359 360 36 I 362 J.A. Orcutt Report DOE/ NV/00410-70 1982 INIS Atomindex Abs. No. 749174 1983. J. T. McVey C. Campuzano and D. E. Fowler Nucf. Chem. Waste Manage. 1981 2 197. A. C. Gray and D. F. C. Morris Radiochim.Acta. 1982 31 153. V. G. Polyukhov G. A. Tirnofeev and A. A. Elesin Radiokhirniya 1982 24,494. V. G. Polyukhov G. A. Timofeev V. V. Kalygin and P. A. Privalova Radiokhimya 1982 24 490. E. Akatsu Radioisotopes (Tokyo) 1982 30,647. Z. N. R. Baptista M. S. M. Mantovani and F. B. Ribeiro An. Acad. Bras. Cienc. 1981 53 437. A. N. Murin S. 1. Bondarevskij and V. V. Eremin Radiokhimiya 1981 23 933. D. C. Walker J. Phys. Chem. 1981 85 3960.

ISSN:0260-1818    

DOI:10.1039/IC9838000325

出版商:RSC    

年代:1983

数据来源: RSC

摘要:

14 Industrial Chemistry The Fertilizer Industry in the Year 2000* By K. GILBERT The British Sulphur Corporation Ltd. Parnell House 25 Wilton Road London SWl V 1NU 1 Introduction Making forecasts is a chancy business. Making any forecast presupposes a precise knowledge of today and the past an unlikely circumstance in itself. Taking a view in 1984 of a particular industry in the year 2000 a look ahead of 17 years has the advantage that the forecast will be forgotten well before it can be compared with what really happened. But will it? Forecasts are being made all the time. A view based on the best possible knowledge is better than no view to a company considering a major investment (or even survival itself) or a government considering its medium term financial strategy.Economists market researchers futurologists and others are all involved in what was once the province of the soothsayer and the astrologer. We still have those as well and they are still as right and as wrong as they always were. To get back to fertilizers and the examination of past forecasts. In October 1964 Ignatieff Doyle and Couston of the FAO Rome presented a paper to the Fertilizer Society entitled ‘Future Fertilizer Requirements of Developing Countries and Crop Response to Fertilizer in these Countries’.’ The authors did what I am now doing. They compared a forecast made by an FA0 committee in 1946 for 1960 with the actual outcome. The total consumption of N and P205was forecast (over a period of 14 years) with considerable accuracy but the regional forecasts were wide of the mark.The authors also gave figures for P,05 consumption comparing a forecast for 1959/60 made in 1953 (a period of 6 years) and once again the regional figures were wide of the mark. Having shown that their own past forecasts were wide of the mark they bravely set out to comment on 1980 consumption. I am not being fair to the authors because what the FA0 stressed then and now are nutritional goals. Fertilizer consumption then becomes a consequence of the goals taking into account the amount of land available cropping pattern and so on. The authors quote figures prepared by their colleague Parker. He calculated that in order to meet food requirements in 1980 fertilizer use had to increase in four developing regions to the amounts shown in Table 1.* Based on a lecture given at the Annual Chemical Congress of the Royal Society of Chemistry University of Exeter April 1984. ’ Proceedings No. 83 The Fertiliser Society London 29th October 1964. 345 346 K. Gilbert Table 1 Estimated fertilizer requirements for 1980 nutri-tional goals (million tonnes plant nutrients) Fertilizer consumption Region 1959/60 1980 Asia and Far East 2.53 20.0* Near East 0.25 3.6 Africa 0.40 8.6 Latin America 0.82 7.3 4.00 39.5 * Includes 5.0 millions for Mainland China We now have figures for fertilizer years 1979/80 and 1980/81 for comparison although the definition of the regions is a little different (Table 2). Table 2 Fertilizer consumption (million tonnes nutrients) Forecast Actual Region 1980 1979/ 80 1980/81 Asia and Far East 20.0 -3.6 -Near East Asia" -13.186 13.402 Other Communistb -14.1 19 16.406 Africa 8.6 2.819 3.265 7.3 -Latin America Central America' -1.707 3.528 South America -4.6 18 5.292 Total 39.5 36.449 41.893 a Excluding Communist Asia.Excluding USSR Eastern Europe but including Cuba. Excluding Cuba. The average of years 1979/80 and 1980/81 was 39.171 million tonnes and so the out-turn was remarkably close to the perceived need-less than 1% out over 20 years. The authors also examined a forecast made by Steward.2 He based his estimates on a high standard of nutrition and he predicted that world consumption of fertilizers Table3 Fertilizer consumption (million tonnes) of N P205 and K20 in 1960 and estimated consumption in 1970 and 1980 in three selected areas of the world Compounded rate of Estimated 1960 increase O/O consumption Area Consumption 1960-1970 1970-1980 1970 1980 Developed countriesa 20.0 3 3 26.9 36.1 E.Europe and USSR 5.0 12 5 15.5 25.3 Developing countriesb 2.7 15 10 10.9 28.3 World 27.7 6.8 5.3 53.3 89.7 a Includes USA Canada Western Europe Oceania and Japan. Includes all countries of Latin America Near East Far East and Africa except Mainland China and Japan ' D. D. Steward 19649 Foreign Agriculture I1 No. 19 U.S.D.A. Washington D.C. 34. Industrial Chemistry The Fertilizer Industry in the Year 2000 would reach 90 millon tonnes of plant nutrients by 1980.The FA0 authors pointed out that this estimate required a 15% p.a. annual increase in fertilizer use in the developing countries between 1960 and 1970 followed by an annual 10% p.a. increase between 1970 and 1980. They felt that this was a very optimistic view. Steward's figures are given in Table 3 We compare his forecast for world total with the out-turn in Table 4. Table 4 Fertilizer consumption 1970 and 1980 (million tonnes nutrients) Forecast Actual i 970 1980 1970" 1980' 53.3 89.7 66.2 109.4 Average of Fertilizer years 1969/1970 and 1970/1971. Average of Fertilizer years 1979/1980 and 1980/1981 What appears to have thrown out these forecasts was an incorrect view of the potential growth in the developed world and Eastern Europe. The compound rate of growth for the developed countries was forecast at 3% p.a.over the 20 year period but growth was much faster than this. By 1970/71 Western European and North American consumption combined had reached 33.5 million tonnes and it was 44.4 million by 1980/81. In Eastern Europe and the USSR the 1970/71 consumption was 18.5 million tonnes compared to the forecast of 15.5 and by 1980/81 consump- tion had reached 30.1 million tonnes compared to the forecast of 25.3 million tonnes. The developing world did not do at all well. Our consumption statistics show that the group consisting of Africa Central America South America and Asia (but not including the Communist countries) which is roughly comparable with Steward's developing countries in Table 3 reached a consumption of 10.4 million tonnes in 1970/71 and 25.5 million tonnes in 1980/81.This preamble has allowed me to say something about forecasts but it also serves to show what strides were made by the fertilizer industry from the late 1940s to 1980. Turning to my own view of the future I intend to deal with the subject as follows. First I will give a picture of the fertilizer industry as it exists today then I will try to describe the industry in the year 2000 in terms of size location ownership size of plants technology and finally trade. 2 A Picture of the Industry as it Exists Today The World Fertilizer Industry is a very large business. In terms of the three major nutrients -nitrogen (N) phosphorus (P20,) and potassium (K20) it accounts for about 1 14 million tonnes of consumption.The fertilizers that are used vary in nutrient content but it is reasonable to assume that 250-300 million tonnes is handled in product terms. This scale of production requires multi-million tonnes of raw materials-hydrocarbons phosphate rock sulphur and potash. World-wide there are about 6500 plants making fertilizers. These plants do not include the large number of blending plants making both solid and liquid products that are a particular feature of the North American fertilizer scene. 348 K. Gilbert An analysis of consumption shows that Western Europe and North America have declined in importance (in percentage terms) as other regions have grown in importance. The present situation is given in Table 5.Table 5 Fertilizer consumption by region and nutrient 1982/83 (Preliminaryjigures) ( thousand tonnes) N p20 K2O Total Western World 33 863 17 971 13 594 65 401 Communist World 27 147 12 410 9 045 48 652 Western Europe 10 514 5 664 5 072 21 205 Africa 1 809 1072 346 3 227 North America 9 368 4 366 4 757 18 491 USSR 8 908 5 616 4 961 19 485 Eastern Europe 5 343 3 472 3 422 12 246 Other Communist 12 946 3 319 662 16 927 Central Americaa 1461 526 167 2 154 South America 1184 1518 1038 3 740 Asiab 9 228 3 796 1 969 14 993 Oceania 272 1 029 242 1 543 a Not including Cuba. Not including Communist Asia The basic raw materials for the fertilizer industry are hydrocarbons with natural gas being the most important for ammonia production; phosphate rock for the production of single superphosphate phosphoric acid and triple superphosphate ; sulphur for the production of sulphuric acid and thence phosphoric acid; and potash.Ammonia phosphoric acid and sulphuric acid can be considered as inter- mediates. Some phosphate rock having the right solubility characteristics is used directly as a fertilizer. The main products are as follows Ammonia.-Natural gas is the most important hydrocarbon raw material for ammonia production but naphtha fuel oil and coal can also be used. The electrolysis route avoids the direct consumption of hydrocarbon entirely if the power is generated in a nuclear or hydroelectric plant. Natural gas is converted into hydrogen and carbon dioxide and the hydrogen is combined with nitrogen to give ammonia.All the process stages are catalysed and are carried out at elevated temperature and/or pressure. The production of 1 tonne of ammonia requires 32-42 million Btu natural gas or 0.9 tonne naphtha or 1.9 tonnes of coal. Urea.-Carbon dioxide usually from the ammonia process is reacted with ammonia at elevated temperature and pressure to give a solution of urea which is evaporated to give solid urea or is used in the preparation of UAN solutions. The production of 1 tonne of urea requires 0.58 tonne ammonia and 0.76 tonne carbon dioxide. Ammonium Nitrate (AN).-Ammonia is oxidized over a catalyst at high temperature to give nitric acid. Nitric acid is neutralized with ammonia to give AN solution which is evaporated to a melt which is then granulated.1 tonne of AN requires 0.78 tonne of 100% nitric acid and 0.21 tonne anhydrous ammonia. Industrial Chemistry The Fertilizer Industry in the Year 2000 Ammonium Sulphate (AS).-Most AS arises as a by-product in caprolactam manufac- ture and from the removal of ammonia from coke oven gas. Small amounts are made directly from ammonia and sulphuric acid. 1 tonne AS requires 0.26 tonne ammonia and 0.74 tonne sulphuric acid. Nitrogen Solutions.-Combinations of urea and ammonium nitrate (UAN) ammonia and AN and ammonia and urea have become major sources of nitrogen for agriculture. The most popular combination is a mixture of AN and urea in proportion to give maximum solubility (approximately 45% AN 35% urea and 20% water containing 32% nitrogen).Single Superphosphate (SSP).-Made by mixing pulverized phosphate rock with sulphuric acid allowing to set and cure and then crushing and sizing. Although easy to make it has a low nutrient content which increases its cost of transportation per unit P205. 1 tonne SSP of 20% P205 content requires 0.64 tonne phosphate rock 70% BPL (32% P205) and 0.37 tonne sulphuric acid 100%. Phosphoric Acid.-As far as the fertilizer industry is concerned most phosphoric acid is made by the wet process involving the acidulation of phosphate rock with sulphuric acid followed by filtration to remove the calcium sulphate (phosphogyp- sum) liberated. The solution of phosphoric acid is then concentrated to the desired level which for so-called merchant acid is 52-54% P205 and for superphosphoric acid is 68-72% P205.Phosphoric acid can also be made by burning phosphorus (made in an electric furnace) and by acidulating phosphate rock with hydrochloric acid. These generally more expensive routes result in a high quality acid suitable for industrial applications. The production of 1 tonne P205 as phosphoric acid by the wet process requires about 3.3 tonne phosphate rock 70% BPL (32% P205) and 2.8 tonnes sulphuric acid 100°/~. Triple Superphosphate (TSP).-Made by treating phosphate rock with phosphoric acid. The process is similar to that for SSP but TSP has a much higher P205 content of 44-46% and is therefore a more attractive commodity in international trade. 1 tonne of TSP of 46% P205 content requires 0.40 tonne of phosphate rock 70% BPL (32% P205) and 0.85 tonne of phosphoric acid 40% P205(0.34 tonne P205).Ammonium Phosphates.-Diammonium phosphate (DAP) is the most popular prod- uct of this type but a range of compositions can be made depending on the proportions of ammonia and phosphoric acid used. 1 tonne of DAP requires 0.23 tonne ammonia and 1.175 tonne phosphoric acid 40% P205(0.47 tonne P205). 1 tonne monoammonium phosphate (MAP) requires 0.15 tonne ammonia and 1.35 tonnes phosphoric acid 40% P205(0.54 tonne P205). Nitrophosphates.-Acidulation of phosphate rock with nitric acid converts the insoluble phosphate into a soluble form (the object of all the acidulation processes) and also produces a product that contains nitrate nitrogen.Phosphoric acid is not produced as such. The choice of a nitrophosphate route depends on many factors but an important consideration is the cost and availability of sulphur as compared to the cost and availability of hydrocarbon feedstock. 350 K. Gilbert Potash.-Potash minerals are mined or are recovered from dry lakes and salt lakes. The most common minerals are sylvinite (mined) langbeinite (mined) and carnalite (salt lakes). The potash (potassium chloride) is liberated and separated from common salt or magnesium chloride by a variety of methods including sizing flotation heavy media separation electrostatic separation and crystallization. Non-chloride Potash.-In most fertilizers potassium chloride can be used and is the cheapest form of KzO.Potassium sulphate and nitrate are preferred for some crops. They are usually made from KCl using sulphuric acid and nitric acid respectively although potassium sulphate does occur naturally in minable deposits and in certain salt lakes. The volumes are small compared to potassium chloride. Sulphur.-Sulphur is a key raw material for phosphoric acid and SSP production. It is also in its own right an essential plant nutrient. Whilst most sulphur is burnt to give sulphuric acid not all sulphuric acid is made from sulphur. Smelter acid is an important source for the fertilizer industry and in certain locations sulphuric acid from pyrites is important. It is a matter of concern (economically and environ- mentally) to the phosphate fertilizer industry that the sulphur used in producing phosphoric acid ends up as calcium sulphate waste.In addition to the main nutrients N P and K there are less important nutrients in volume terms that are just as important to the well being of the plant crop. These are calcium magnesium boron copper iron manganese molybdenum and zinc. A deficiency of any one can adversely affect the plant even though the other nutrients are available in sufficient amount. 3 Size of the Industry We have already given a view of the present size of the industry. This section deals with its growth prospects to the year 2000. The Fertilizer Industry exists as a means to an end; the end being food production and to a much lesser extent production of other agricultural products such as fibres.At the present time large numbers of people are inadequately fed whilst at the same time agricultural surpluses arise in the developed world. The problem is not just one of inadequate global food production but arises from the inability of some people to buy food and to move it from areas of surplus to areas of need. Even this is an oversimplification. To supply a starving people with food is common humanity but in the longer run to help them grow their own food is preferable. The supply of finance for fertilizer purchase is receiving the attention of agencies such as the World Bank. In some circumstances this assistance can be much more helpful than a larger sum for the construction of a fertilizer plant. A recent report prepared for the U.N.World Food Council says that some of the dire predictions made a decade ago about world food scarcity were wrong and the threat of a global food crisis now seems remote. The change of mind is due to a substantial recovery in world cereal production and the resulting downwards pressure on grain prices. Nevertheless new mouths have to be filled and so population growth has to be taken into account in long-term fertilizer forecasting. Industrial Chemistry The Fertilizer Industry in the Year 2000 351 By the year 2000 a world population of 6 billion is probably ine~itable.~ The lowest level is 5.9 billion. These increases represent a compound growth rate of 1.44-1.82% p.a. The compound growth between 1950 and 1980 was 1.89% pea.and between 1970 and 1980 1.83% p.a. Fertilizer consumption in nutrient terms increased at an average rate of 5.41% p.a. between 1970/71 and 1980/81. It would appear that the Fertilizer Industry had no difficulty in keeping well ahead of population growth and we have no reason to suppose why it should not do so up to 2000. However the need for fertilizer growth on a per capita basis is greater in the developing world than in the developed world. Population growth in the develop- ing world from 1980 to the year 2000 is forecast at about 2.04% p.a. compound. Apart from population growth two important factors are arable land availability and cropping intensity. In the FA0 study ‘Agriculture Toward 2000’ it is estimated that 72% of the required increase (in agricultural production in developing countries) will have to come from the intensification of existing agriculture and 28% from the expansion of arable land.4 The FA0 suggest that by 2000 arable land in use will increase by the amounts shown in Table 6.Table6 Availability and use of arable land in the developing countries Arable area in use as a YO of potential area Region Current 2000 Africa 30 39 Far East 79 87 Latin America 25 39 Near East 63 67 Developing countries 40 50 Source FA0 Other factors of importance in agricultural production are water availability the provision of better seed research crop protection (standing crop and stored produce) power and energy the provision of advisory services and the availability of finance.Farmer income has a strong bearing on fertilizer use. At the subsistence level the farmer does not use any fertilizer. At the sophosticated farmer level for example in the USA some farmers will cut back on fertilizer application levels if low crop prices are expected. Future demand for fertilizers can be affected to a great extent by a change in the USA situation. A 10% change in consumption in North America is equivalent to over 2 million tonnes of nutrients more than the total used in Oceania and about the same as the total used in Central America. In 1982/83 nutrient consumption in North America was 4.895 million tonnes down on the usage level of 2 years previously. This is roughly equivalent to a loss of 1 year’s growth on a world basis.Sources FA0 and The Global Report to the President ‘Entering the twenty-first century’ Penguin Books 1982. J. W. Couston ‘World Food Production and Fertilizer Demand Prospects’ FAO Rome International ‘Sulphur ’82’ Conference Proceedings British Sulphur Corporation London 14-1 7 November 1982. 352 K.Gilbert The availability of manufacturing capacity is unlikely to be a constraint to fertilizer consumption other than in the short term. Any impending shortage would raise price expectations and make investment in new capacity more worthwhile. The one exception may prove to be the nitrogen sector in the medium term where the rate of plant building may not keep up with demand. In developing countries with cheap gas it can take 7-10 years to plan a project organize finance and build a plant.Raw material availabilities need to be considered. All the basic raw materials should be available at a price. Phosphate rock and potash are plentiful although a gradual move to lower-grade deposits will increase production costs Hydrocarbon sources for ammonia production will be costed in terms of their fuel value and the average cost into ammonia plants will rise in real terms but there is no reason to expect a general shortage of feedstock. The only question mark is against sulphur supply which is also largely fuel related as more and more arises from oil refinery desulphurization processes and sour-gas processing. Sulphur supply and demand will be in a delicate balance in the early years of the forecast period but may have eased slightly by the early 1990s as USSR production increases substantially.The remaining question is can any technological changes significantly affect fertilizer demand in the period to 2000? The most talked about is nitrogen fixation. Professor Postgate of the Agricultural Research Council Unit of Nitrogen Fixation at the University of Sussex has recently reviewed the prospects.’ His conclusion is that major commercial exploitation of current and very interesting laboratory experi- ments could be made in the time frame of ‘a few years’ for augmenting the effectiveness of existing symbiotic systems by genetic manipulation to ‘two to three decades away’ for somatic hybridization. He points out that there are immediate and short-term possibilities involving an expanded production of legumes such as soya beans the winged bean chickpeas and lupins.Azolla a water fern which harbours nitrogen-fixing cyanobacteria is showing potential as a green manure in tropical agriculture and in particular in rice production. Despite these developments the effect on industrial nitrogen fertilizers in the forecast period is expected to be minimal. A significant downward trend in nitrogen demand might be expected when efficient diazotropic associations with cereals are developed by genetic manipulation but this stage might only be reached in the early part of the 21st Century. Questions as yet unanswered have been raised about the energetics of these systems. The nitrogen fixation mechanism has to be fuelled by the plant and so there could be a corresponding yield loss.It may be more effective to use nitrogen fertilizers after all A new study only a brief review of which we have seen concludes that innovations in plant genetics will add $5 billion a year to the value of major crops over the next decade an amount that will climb to $20 billion a decade later. The report forecasts that world food production 25 years from now would rise 5-10% as a result of biotechnology alone. J. R. Postgate FRS ‘Probable Impacts of Biological Nitrogen Fixation on Fertilizer Use’ ‘Fertilizer ’83’ Conference Proceedings British Sulphur Corporation London 13-16 November 1983. ‘The New Plant Genetics’. Report by L. William Teweles and Company Milwaukee USA reviewed in 7he New York Times 8 December 1983.Industrial Chemistry The Fertilizer Industry in the Year 2000 Taking all these factors into account we forecast increases of nutrient consumption to the following range by 2000 (million tonnes) 19821 83 2000 '% change N 6 1.03 112-1 18 83.5-93.3 p205 30.38 55-58 8 1.O-90.9 K2O 25.00 (1982) 4547 80.0-88.0 These increases are equivalent to the output of 170-190 new plants for ammonia production and 147-164 new plants for phosphoric acid production. Two points have to be borne in mind. In the early years of the period some of the extra requirement will come from existing capacity. Then the closure rate of old and inefficient plants has to be taken into account. This is particularly the case with ammonia where energy efficiency is such an important factor bearing on cost of production.This indicates that a substantial building rate of about 10 ammonia plants and 9 phosphoric acid plants a year is required. 4 Location of the Industry The trend over recent years has been for the production of basic fertilizer materials to move towards raw-material sources and towards the developing world. Sometimes these factors are coincident and reinforcing. They also have a bearing on the pattern of trade. These trends are likely to continue. The trend towards conversion of raw materials in the countries in which the raw materials are found rather than shipping the raw materials as such is a natural development. The raw materials have a low value. Conversion into an intermediate product enhances the value of the basic resource and the income arises in the country of conversion and more people are employed.A country shipping phosphate rock at say $35 per tonne f.0.b. can convert the rock into phosphoric acid to sell at $300 per tonne P205f.0.b. As about 3.3 tonnes rock is required for 1 tonne P2O5 about $185 is available to purchase other raw materials and to pay for the conversion into phosphoric acid. The move of basic production to the countries with a strong raw material base is shown most clearly for phosphoric acid. Morocco an important rock supplier particularly to Europe has made massive investments in phosphoric acid plants and is shipping increasing amounts of acid. Over the period 1971-1982 Moroccan rock production increased by 48.7% and exports increased by 17.6% but exports peaked in 1974 and have since fallen by 25.2%.In the same period phosphoric acid production increased by 792.9%. Tunisia is the second largest phosphate rock producer in Africa. It too has increased its phosphoric acid production at the expense of rock exports. Over the period 1971 to 1982 Tunisia increased its rock production by 32.7'/0 its rock exports declined by 1 11.6% but its phosphoric acid production increased by 456.9%. Two other phosphate rock producers in the developing world Jordan and Brazil also processed more of their own rock. Jordan (the largest rock producer in Asia) 354 K. Gilbert and Israel have only recently started up wet phosphoric acid production using sulphuric acid.Brazil was a substantial importer of phosphate rock and phosphoric acid. Rock imports peaked at 1.556 million tonnes in 1977 and phosphoric acid imports peaked at 0.818 P205 million tonnes in 1980 having increased from about 22000 P205 tonnes in 1971. By 1982 acid imports had fallen to 0.317 million tonnes. Western Europe has traditionally been a strong manufacturer of fertilizers includ- ing phosphate despite its weak raw-material position particularly for phosphate rock. It has been able to buy rock from North Africa Togo Senegal USA USSR and Israel for conversion into phosphoric acid and other phosphate intermediates. The region is likely to remain an important rock consumer through to 2000 although rock imports are now at best stagnating whilst phosphoric acid imports continue to grow steadily.My colleagues Kurtanjek Park and Phillips in a paper to The Fertiliser Society in 1983’ wrote ‘It can be clearly demonstrated that vertically integrated ( i.e. rock-mine based) producers of P205intermediates and fertilizer products and especially those whose mining/manufacturing facilities are state-owned enjoy cost advantages deriving from their control of the mineral raw materials in particular of phosphate rock which prima facie would make their competitive strength irresistible and sound the death-knell of primary P205 manufacture in West Europe’. My colleagues were looking ahead to 1990. Despite the apparent inevitability of a decline in basic phosphates production in Western Europe they concluded their paper with the view ‘... that notwithstanding the irreversible demise of West Europe as a major factor in world P,05 export markets the West European phosphate fertilizer industry which with few exceptions is integral with the West European nitrogen industry will maintain its dominant position in the domestic markets and whilst benefitting from the increased availability of competitive liquid and solid P205intermediate supplies on the world market to enhance its profitability it should not be expected completely to succumb to pressure from the vertically integrated (rock-mine based) P205producers. It will not however be able entirely to resist inroads from this quarter’. Ammonia production-location changes are more difficult to predict.Natural gas is found in all regions and ammonia manufacture is only one option for its utilisation. Gas arising in an area of low demand can be moved to customers in other areas by pipeline or ocean-going vessel. Alternatively the gas can be converted into ammonia or urea for shipment. The production of methanol is another alternative. Out of a 1982 world production of 76.9 million tonnes ammonia (as N) only about 5.6 million was traded internationally. The largest net exporter in 1982 was the USSR but their exports of 1.407 million tonnes only amounted to 9.2% of their production. If ammonia projects are considered then the trend is for more of them to be located in the developing world in which we include China and the USSR.Of the ’ M. P. Kurtanjek M. N. Park and T. D. Phillips ’Manufacturing Versus Importing A Techno-Economic Review of the Outlook for the West European Phosphate Industry’ Proceedings No. 214 The Fertiliser Society London 21st April 1983. Industrial Chemistry The Fertilizer Industry in the Year 2000 59 plant projects which we list as under construction contracted and bidding (50% likelihood) with a total capacity of 16.46 million tonnes 37 plants with a total capacity of 8.724 million tonnes are in the developing regions of Africa South America and Asia and a further 13 plants with a total capacity of 5.156 million in Eastern Europe. Nitrogen is the basic nutrient and one that must be used every year. All agricultural countries need an assured source of supply and often see an ammonia plant as a strategic necessity.In these circumstances the raw material situation is of less importance and a political rather than economic decision may be made. Political factors are not absent from the West European and US scenes. The pricing of gas is crucial to the future of the ammonia business in a free-trade world. Governments decide the price of gas either directly or through their taxation policies or through their regulatory processes as in the USA. One decision would keep ammonia production in West Europe another would result in its decline. 5 Ownership There are two main trends as far as basic production is concerned. The first is that the competitiveness of the business a need for rationalization and a desire for a basic raw-material position is leading to fewer and larger companies in the Western World.The second is that more and more of the fertilizer industry is government owned. Regarding the first we have seen its effects in recent years in the UK with the take-over of Fisons by Norsk Hydro and that of Albright and Wilson’s fertilizer operations by ICI. Other small companies have been absorbed and we are left with three.. . ICI Norsk Hydro and UKF. The French industry seems to be under constant reorganization. The Spanish industry is facing a major reorganization. In both these countries in the future there will be fewer plants and less competition amongst the domestic companies (probably state organisations) that remain. Nine8 has suggested that the ideal number of producers supplying a homogeneous market is three but it is hard to imagine the EEC for example being supplied by three fertilizer companies.The second trend is towards state ownership. Sheldrick’ in the Thirteenth Francis New Memorial Lecture to the Fertiliser Society pointed out that the percentage of fertilizers produced in developed economies would fall to about 43% of the world total by 1990 from about 76% in 1950 whilst production in centrally planned economies would increase to 36% from 19% and in developing economies to 21‘/o from 5% over the same period. As we know much of the industry in developed economies is in state hands with only the large USA industry uniquely private. By 1990 a minimum of 66% of the world industry will be state owned and with the higher growth-rate in the developing world the trend is likely to continue through the 1990s so that by 2000 70% or more will be state owned or controlled.This trend in ownership has implications for trade. An increasing emphasis on government to government deals and barter deals is likely. This would result in a * C. H. Kline ‘Profit Strategies in World Chemicals’ Hyurocurbon Processing January 1984 W. F. Sheldrick ‘The Changing Structure of the International Fertilizer Industry’ Proceedings No. 212. The Fertiliser Society London 17th March 1983. 3 56 K. Gilbert further limitation of free trade although as Sheldrick says it might also add beneficial stability to a market which is subjected to cyclical crises.6 Size of Plants Over the years chemicals plants have got bigger. During the 1960s there was almost a cult of bigness in the chemical industry. I remember many presentations on the economies of scale. A greater realism prevails today. Certainly capital costs per tonne of capacity are lower as plant size increases but the costs of not operating a large plant at a high utilization are daunting and to have one idle for any length of time can be disastrous. The situation in the fertilizer industry is that plant sizes on a single-stream basis are reaching a practical limit and it seems unlikely that we will see a significant change in unit sizes in the period up to the year 2000. The average size of plants in operation will increase however as new large plants are constructed and old small plants are retired.From our computer data-base of fertilizer plants we have made an analysis for two basic fertilizer products ammonia and phosphoric acid. In the fertilizer year 1967/68 there were 463 ammonia plants with a total operating capacity of 41 018 000 t.p.a. Thus the average size was 88 590 t.p.a. (277 t.p.d.). North America had the highest average at 102480t.p.a. and Oceania the lowest at 27 000 t.p.a. By 1982/83 the number of plants had increased by 15.6% to 535 but the total operating capacity had increased by 152.5% giving an average size of 193 600 t.p.a. (605 t.p.d.). The most marked change was in Asia. In 1967/68 91 plants had an average capacity of 68010 t.p.a.In 1982/83 121 plants had an average capacity of 247 620 t.p.a. The extent of the change for phosphoric plants is similar. In 1967/68 there were 186 phosphoric acid plants with an aggregate operating capacity of 10 142 000 t.p.a. and an average capacity of 54 200 t.p.a. By 1982/83 there were 278 plants (an increase of 49.5%) with a total capacity of 31 918 000 t.p.a. (an increase of 214.7%) and an average capacity of 114 810 t.p.a. (an increase of 11 1.8%). A consideration of projects which were under construction or contracted as at February 1984 shows that for ammonia there were 50 with a total nameplate capacity of 14 487 000 t.p.a. and an average capacity of 289 740 t.p.a. (905 t.p.d.). The largest plants in this project category were of 407 000 t.p.a.(1272 t.p.d.). The number of ammonia plant projects at the bidding stage in February 1984 was 9 with an average capacity of 219 220 t.p.a. In addition there were 56 plants with an average size of 281 690 t.p.a. at the study stage. The equivalent numbers for phosphoric acid projects are (thousand tonnes) Total Average No. plants capacity capacity Under construction and contracted 22 330 1 150.05 Bidding stage 4 658 164.50 Study stage 33 6458 196.70 Industrial Chemistry The Fertilizer Industry in the Year 2000 Most of the plants at the bidding and study stages should be built well before 2000 and there will be others built before that time which have not yet been considered at all. There will be a considerable number of retirements of old plants.It is reasonable to assume that these will be usually of less than average size. In the case of ammonia the average size of the plants in operation in the year 2000 should be about 275 000 t.p.a. It will not always be possible to build the largest plant (gas supplies in a particular location may be limited or there may be market constraints) but we have assumed that most will be of the largest size. The same reasoning applied to phosphoric acid results in the conclusion that the average size in the year 2000 should be about 165 000 t.p.a. As with ammonia we have assumed that most plants built in the 1990s will be of the largest practical size that is over 700 t.p.d. There is an argument that there is a place for relatively small ammonia plants.Plants of 400 t.p.d. or less possibly as small as 10 t.p.d. could use simple technology with reciprocating compressors and could be designed and constructed by Third World engineering companies such as those in India. If the small plant was located in a situation close to its market and was protected from competition either by government regulation or by its distance from alternative supplies then it could be viable. U.N.I.D.O. has been a focus for these ideas but it has to be said that there are many sceptics. In this section we have been concerned with basic production units where chemical processes are carried out. The ready availability of the granular products of these units -MAP DAP TSP urea -together with granular potash encourages the trend towards relatively small blending units.These units consisting of raw material and finished product storage and simple mixing equipment are inexpensive and their operation can give a high level of service to farmers in their immediate vicinity. This type of operation is very well developed in the USA where many blenders also handle pesticides and liquid fertilizers and apply tailor-made formulations. As the basic plants get bigger we will almost certainly see at the interface between the fertilizer industry and the farmer more of these smaller companies depending for their success on a good knowledge of their market area and rapid response to the farmers’ needs. 7 Technology Fertilizer technology is a very complex matter and the subject of hundreds of papers each year.A series of detailed monographs would be needed to do it justice. In this section some of the main trends are briefly described. The first is the trend towards energy efficiency. This is most marked in ammonia technology but is also important throughout the industry. The Fertiliser Institute Washington DC carry out an annual Energy Use Survey of the US Fertilizer Industry. Their figures for the average energy requirement for manufacturing ammonia in centrifugal plants are given in Table 7. The energy requirement figures are in the range 10.79-11.21 Gcal/tonne. Pro- cesses are available for plants which would operate at an energy efficiency of 7.0 Gcal/tonne but these are not fully proven designs ie. operating experience is very limited.7.0 Gcal/tonne probably relates to battery-limits gas usage in LHV 358 K. Gilbert Table 7 Ammonia manufacture -Energy requirements* ( 1000 Btu/ tonne) 1979 (Based on 10 387 37 1 tonnes production) 44 473 198 1 (Based on 1 1 8 15 294 tonnes production) 42 969 1982 (Based on 8 734 464 tonnes production) 42 834 * Total energy requirement including start-up shut-down catalyst reduction and fuel for turbine and engine driven compressors or pumps. The natural gas require- ment excluding start-up shut-down and catalyst reduction amounts to about 95% of the above figures. Source TFI units (lower heating value) the usual way that contractors quote gas usage. Natural gas is normally sold on the basis of HHV (higher heating value) and plant operators normally refer to gas conversion on this basis.LHV is about 90% of HHV. Where gas is very cheap the operator might well go for a proven and reliable design with a somewhat higher gas usage. Where gas is expensive the low gas usage design will be considered but reliability remains very important. The choice of ammonia plant technology has recently been reviewed by Brown." My own company has reviewed the subject of revamping ammonia plants" to improve energy efficiency and therefore reduce operating cost. Energy savings are also possible in phosphoric acid manufacture. In the USA the energy requirement to manufacture filter-grade acid ranges from 2402-3 129 thousand Btu/tonne P20 and it requires a further 5084 thousand Btu/tonne P205 on average to convert filter grade into merchant grade 54%.The concentration is usually accomplished by using steam from an on-site sulphuric acid plant. Most phosphoric acid is made by the dihydrate process. This process requires approximately ten times as much low-pressure steam as does a plant operating a hemihydrate process (per tonne P205 as 54% P205 strength). This is an attractive saving if an oil coal or gas-fired boiler is used to generate the steam or if the steam is generated in a sulphuric acid plant and can otherwise be sold or if the sulphuric acid plant cogenerates electricity. Sulphuric acid production is an important and often integral part of the phosphate fertilizer business and many of the latest plants haive cogeneration facilities.The heating value of a tonne of sulphur is equivalent to that of 2 barrels of oil. In early 1982 Monsanto compared the cost of a new technology 1980s plant and a mid-1970s plant based on a capacity of 1,800m.t./day in a phosphoric acid complex. The capital cost of a new early 1980s plant at that time was $25 million compared with $21 million for a plant using mid- 1970s technology. Adding the turbogenerator would cost $5 million for a total capital cost of $30 million. But the plant could generate 15 000 kW for sale with a value of $6 million/year. All costs were based on 1981 dollars. After a period of stability during the recession energy costs are likely to begin to rise again as business activity picks up. The cost increase for oil and gas may well lo F.C. Brown 'Ammonia Plant Preferences in the 1980s' Proceedings No. 218. The Fertiliser Society London 19th October 1983. 'Revamping Ammonia Plants Improve Process Operation and Economics'. Supplement to Nitrogen No. 141 January-February 1984. Industrial Chemistry The Fertilizer Industry in the Year 2000 be higher than general inflation. In any case as we have shown savings in energy can lead to substantial cost savings at today’s oil and gas prices and so the fertilizer industry and plant designers will continue to look for economies. The second trend of note is that leading to a greater tonnage of blended fertilizers made by simple mixing. ‘Bulk blends’ are mixed fertilizers where no chemical reactions occur between the raw materials.They are thus distinct from granular products where chemical reactions and/or melting take place during the mixing and granulation stages. The latter method results in storage stable fertilizers. In past years simple mixing did not give satisfactory products. Dusty materials with a tendency to segregate and cake were the norm. These inferior products were quickly replaced by granular fertilizers. The situation has now changed in that raw materials of consistent and appropriate granulometry are available for bulk blending and it is recognized that in many circumstances bulk blending is preferable to granulation. According to Taylor,’* bulk blends account for approximately 70% of the solid compound fertilizers sold in the USA today. The number of bulk blending plants in the USA has increased from 450 in 1960 to 8000 in 1983.Taylor believes that bulk blending will be the first production alternative selected in many developing nations. The main reason is the lower capital cost requirement. Taylor cited a capital charge (depreciation) per metric tonne of fertilizer over a 10 year plant life of about $10 for a chemical granulation complex ($7-10 million investment) and about $3 for bulk blends ($2-3 million investment). A bulk blend plant is simpler to operate than a granulation plant and since bulk blends are free from the process restrictions associated with chemical granulation a wide range of nutrient ratio can be made from a few raw materials. Bulk blends are suitable for incorporating micronutrients and some pesticides.In the section on plant size it is suggested that the other advantage of the local blending plant is the opportunity this gives for a high level of service to the farmer. This factor is likely to become more important as the years go by. Liquid fertilizers have been important in the USA but have made less progress el~ewhere.’~ Liquids can be true solutions or suspensions. The use of liquids is facilitated by the kind of market structure seen in the USA with close contact between the fertilizer supplier (blender) and the farmer. The fertilizer supplier will often apply the fertilizer and so the farmer is relieved of the need to have expensive storage facilities and applicators. In Europe the trend towards liquids has been slow although if ammonia is included then Belgium Denmark France Netherlands and UK consume significant amounts.Apart from anhydrous ammonia the application of which requires special equip- ment and techniques the other fluids which do not require pressurization have some clear advantages over solids. These advantages include ease of handling accuracy of placement (row application or addition to irrigation systems) and suitability for incorporating micronutrients and pesticides. The last can be a big cost saver to the farmer if one or more passes over the field can be avoided. Larry Taylor ‘Increasing Role of Bulk Blending in Developing Nations’ Industrial Minerals Conference ‘Phosphates What Prospects for Growth’ Orlando Florida December 1 1-14 1983.l3 ‘Production and Use of Fluid Fertilizers’ (12 papers from a session with this title). Proceedings of The British Sulphur Corporation’s Second International Conference on Fertilizers ‘Products and Techniques for Plant Nutrient Efficiency’ London 1978. 360 K. Gilbert The initial disadvantage of fluids is the requirement for expensive storage facilities. Granular and blended fertilizer can be stored on the ground under cover but liquids require tanks pumps and valves. This disadvantage is particularly marked in developing countries where it is impracticable to ship and handle small quantities of fluids whereas bagged granular fertilizer can readily be used. For high- value irrigated crops liquid fertilizers are ideal. In some systems fertilizer is delivered to each plant.Israel has pioneered some of these systems known as ‘fertigation’. The composition of the nutrient can be varied with time to give optimum results. The trend to fluid fertilizers might be encouraged by the growing availability of super phosphoric acid which has a concentration of about 72% P,05 and a high level of polyphosphoric acid. This is converted into ammonium polyphosphates which are a good basis for fluid fertilizers. We expect fluid-fertilizer usage to grow at above the rate for total fertilizers over the period to 2000. Despite this solid granular and blended fertilizers will remain the most significant market segment. The final technical trend is that towards greater efficiency of fertilizer use. This trend is being driven by increasing costs of nutrient input and by environmental factors particularly in the case of nitrogen.A range of approaches are being used. Timing and accuracy of application can lead to greater economy of utilisation as was mentioned under the discussion of fluid fertilizers. Where losses of nitrogen are high following fertilizer application as they are with urea in tropical agriculture coating of the granules with a material to retard solution is a possibility. Sulphur- coated urea is a commercial product albeit on a small scale and rubber coatings have been investigated in Malaysia. Sulphur coating has the added advantage that sulphur is an essential nutrient particularly in tropical agriculture. An alternative approach to slow release is to prepare reaction products of urea such as urea-formaldehyde condensates (ureaform) isobutylidene diurea (IBDV) and crotonylidene diurea (CDU).These products are relatively expensive which limits their use to high value crops non-food horticulture and the hobby market. They are used in Western Europe Japan and the USA with production concentrated in West Germany and Japan. The use of nitrification inhibition is another approach. A large number of com- pounds inhibit the nitrosomas bacterium in its conversion of ammoniacal nitrogen into nitrite in the first stage of the nitrification process. In so doing they make the nitrogen available to the plant for a longer period and increase the efficiency of fertilizer use by plants which can otherwise be as low as 50%.Most nitrification inhibitors are applied as coatings to complex fertilizers or as additives to fluid fertilizers. The most well known nitrification inhibitors are dicyandiamide and the propietary products EXTEND (Kalo Laboratories Inc.) and N-SERVE (Dow Chemicals) which have made a significant impact on the North American market. Finally the fertilizer can be fabricated into a super granule. For example urea with a granule size of greater than 10mm has been evaluated in rice fertilization. It is thought that super granules are a more economic method of slowing the release of nitrogen than the labour-intensive mud-ball method of making urea available at a controlled rate to paddy rice. Industrial Chemistry The Fertilizer Industry in the Year 2000 361 Granules of urea between 5-10mm are known as forestry grade and are used in North America and Scandinavia as a forest fertilizer using aerial spreading methods.These techniques and products will be further developed over the next 16 years and should be considerably more important by the year 2000. 8 Trade The move of raw-material producers into the main fertilizer-intermediates ammonia urea phosphoric acid TSP and MAP/DAP has the consequence that trade in these materials increases and that in raw materials declines. This has been mentioned earlier in connection with the location of the industry. The patterns of trade are also changing. Table 8 gives figures for changes in total trade over a 10 year period and show that ammonia phosphoric acid and DAP have increased rapidly.Table 8 Fertilizer materials -total trade 1972-1982 (million tonnes) Compound 1972 1982 growth ('10) Raw Materials Phosphate Rock 43.1 43.4 negl. Sulphur 9.6 14.5 4.2 Intermediates Phosphoric Acid (P,O,) 0.4 2.9 21.9 Ammonia 2.9 6.9 9.1 DAP 3.1 (1976) 5.1 7.4 TSP 2.1 3.0 3.6 Urea 7.0 12.0 5.5 If we look at phosphoric acid in more detail (Table 9) we see that over the period 1971-1982 West Europe East Europe S. America and Asia became substantial importers and Africa (primarily N. Africa but also the Republic of S. Africa) North America and West Europe provided the increased exports. Table 9 Phosphoric acid regional trade ( thousand tonnes) Production Zmports Exports 1971 1982 1971 1982 1971 1982 West Europe East Europe Africa 2733 1029 382 3230 3703 2495 267 - 968 750 - 156 - 552 7 1249 N.America 5047 7675 13 34 90 967 C. America 245 311 - 11 65 75 S. America 76 480 46 3 72 - - Asia 1040 1633 16 788 32 80 Oceania 87 130 - - Trade in phosphoric acid has been growing at a rate of over 20% p.a. compound over a period that Pz05 consumption in fertilizers has been growing at a rate of 3.25% p.a. compound. 362 K. Gilbert As basic fertilizer production continues to move to those countries such as Morocco Tunisia Jordan and the Gulf states where raw materials are plentiful and inexpensive but where the domestic fertilizer markets are relatively small exports will continue to increase at the expense of production in countries (particularly West Europe and Japan) which do not have a raw material position.The cost of phosphate rock in Western Europe to a user is the sum of the cost of production inland transportation and handling in the country of production profit ocean freight and discharge handling and transportation costs in the country of receipt. The integrated phosphate rock/ phosphoric acid producer has a tremendous cost advantage which may amount to more than 50% of the ‘into’ plant cost of a company in say Germany. The advantage that arises to a producer of rock and phosphoric acid is partially offset by the delicate balance required when pricing the two products in a competitive market. The other trend in fertilizer trade has also been mentioned earlier.It is the growing tendency for governments to deal with governments and for barter deals to replace conventional business with money payment. A typical example of the first is the arrangement between Morocco and Poland by which Morocco supplies Poland with phosphate rock in return for sulphur (which is converted into sulphuric acid for phosphoric acid manufacture). It is difficult to see how both sides can benefit in such a deal. The ratio of tonnes phosphate rock to tonnes sulphur has to take account of the market prices of these commodities. If the ratio accurately reflects market prices during the contract period then the only advantage would seem to be that there would be no call on the hard currency holdings of the individual countries.This may be crucial in some cases. The growing number of barter deals has two implications. First it will be a restriction of free trade and secondly it is to the advantage of the few large traders with the financial strength and spread of interests that is required to handle this kind of business. A small trader specializing in fertilizers who is offered copper or rice in payment may have to engage (and remunerate) another trader to place the payment commodity and valuing the business becomes extraordinarily difficult. A large general trader like Mitsubishi in Japan or Cargill in the USA both of whom have offices throughout the world is better placed to switch between commodities. The advantage to the fertilizer buyer would seem to be the elimination of the hard currency requirement but the value of the commodity used for ‘payment’ is almost certainly less than it would fetch for cash.Countries with severe balance of payments positions find barter trading attractive. A very recent barter deal couples Occidental Petroleum Corporation of the USA with Yugoslavia. Occidental will supply goods including coal oil phosphates and animal hides in exchange for as yet unspecified commodities industry products and services from Yugoslavia. Occidental’s deal with the USSR to trade polyphos- phoric acid for Russian ammonia potash and urea is a very well known one in the industry by virtue of the large quantities of materials involved. 9 Summary By the year 2000 the fertilizer industry will be about 80% bigger in terms of tonnage consumption of the three major nutrients N P and K than it was in 1982/83.The Industrial Chemistry The Fertilizer Industry in the Year 2000 proportion of world fertilizer production located in the developing countries will be greater than it is today with particular advances being made by resource-rich countries. Basic production will be in fewer hands and the proportion that is state owned will be higher than it is today. Downstream production of solid and fluid blends will expand with more small operations offering service to local farmers. The average plant size for basic fertilizer materials will increase as new large plants replace old small plants. Plants will become more energy efficient particularly as regards to natural gas for ammonia.Bulk blends will gain at the expense of granular compound fertilizers. Fluid fertilizers will make modest gains and fertilizers will be used more efficiently to maximise uptake by the crop and rninimise losses to the atmosphere and to water courses. Specialized fertilizers will make gains as highly intensive cultivation and agriculture under irrigation increases. International trade in basic fertilizers will increase as a consequence of the movement of production to resource-rich countries. Feeding the world’s growing population requires an efficient and productive fertilizer industry but it must be remembered that fertilizer although essential is only one of the vital inputs to agriculture and food sufficiency. In making the above forecasts we have assumed that progress will be made over a wide front -educational financial health and human happiness.

ISSN:0260-1818    

DOI:10.1039/IC9838000345

出版商:RSC    

年代:1983

数据来源: RSC

摘要:

Author Index Aaseth J. 298 Abaas S. 332 Abad J. A. 243 289 Abazli H. 166 Abdel-Gawad A. S. 342 Abdel- Khalek A. A. 238 Abdelmalik W. E. 342 Abdel-Wahab M. F. 337 Abdesaken F. 84 Abdou Z. J. 47 Abdullaev G. K. 67 Abdullah P. B. 238 Abe T. 327 Abel E. W. 201 274 Aber J. E. 332 Abo El-Khair B. M. 342 Abraham F. 74 186 Abrahams S. C. 299 Abram S.,204 Abram U. 204 Abrams M. J. 204 335 Abronin I. A. 338 Absher J. R. 130 203 Abu-Dan K. 237 Abu-Salah 0. M. 294 Acampora M. 281 Achard J. C. 312 Ache H. J. 328 Acott S. R. 129 193 277 Adam G. 330 Adam H. 284 Adam K. R. 240 298 Adams C. J. 22 Adams E. T. jun. 147 Adarns H. 186 192 202 248 Adarns H. N. 294 Adams J.M. 68 Adams R. A. 252 Adarns R. D. 254 Addison A. W. 130 282 285 Adelskold V. 284 Adlart W. 284 Manas'ev Yu. A. 341 Agha N. H. 337 Agrawal A. S. 339 Agre V. M. 167 Aguila M. I1 Ahmad M. M.,69 Ahmad N. 66 Ahmed F. R. 227 Ahmed K. J. 288 Ahmed S. N. 77 Ahrland S. 275 Aichinger H. 158 Aime S. 240 Ainscough E. W. 212 287 Airoldi C. 296 Ajmir Riahi 288 Aja D. 240 Akatsu E. 326 343 Akimov V. M. 22 Akitt J. W. 62 Akkerman 0. S.,98 172 Aksamentova T. N. 154 Aksenova N. M. 329 Aktalay Y. 109 110 Alagna L. 282 Alam F. 29 Alarcon E. 188 192 Alavi A. 331 Albano V. 128 243 Albano V. G. 258 259 289 Albanov A. I. 154 Albarran G. 340 Albers M.O. 230 Albertin G. 237 Albertsson J. 71 117 Albin M.,316 Albright M.J. 302 Alcock H. R. 230 Alcock N. 241 Alcock N. W. 51 141,265 Alderson P. O. 336 Aleksandrov Yu. A. 22 Alekseev E. G. 337 Alekseev F. P. 73 Alekseev N. V. 56 Alfassi Z. B. 328 Al-Hilli A. M. 337 Al-Hissoni M. H. S.,337 Ali A. A. M. 108 Ali S. A. 328 Aliev F. G. 315 Alinovskaya L. A. 70 Ali-Zade N. Kh. 71 Al-Jibori S.,269 Allain Y.,308 Allan R. M.. 331 Allaoud S. 29 Allard B. 342 Allazov M. K. 71 Allcock H. R. 58 Allen C. W. 112 Allen G. 250 Allen G. C. 319 Almasio M. C. 316 Al-Ohaly A. R. 294 Alper H. 198 Al-Resayes S.-I. 105 267 Al-Samman M. H. 237 Al-Shukri L. M. 331 339 Ama T.205 Aminabhavi T. M. 284 Amira M. F. 238 Amitin E. B. 308 Amma E. L. 299 Ammann D. 11 Amoussou D. 23 24 74 Amuli C. 279 Anast J. M. 286 Andersen N. H. 308 Andersen R. A. 91,317 Anderson A. B. 211 Anderson D. R. 107 Anderson D. W. 328 Anderson G. K. 101 Anderson G. M. 144 Anderson G. P. 282 Anderson M. P. 261 Anderson 0. P. 130 Anderson R. 13 Andersson K. 342 Anderton J. W. 338 Ando F. 104 227 Ando K. 109 Ando W. 86 Andre J. J. 298 AndrCasson L.-E. 203 Andreetti G. D. 233 Andrews L. 147 148 Andrews S. J. 22 Ang K.-P., 286 Angelici R. J. 226 Angelis B. 336 Angleberger P. 337 Anhaus J. 179 Anikiev V. V. 342 365 Author Index Ansell C.W. G. 205 298 Anson F. C. 219 Antolini L. 256 283 Antonio M. R.,194 225 Antonio Abad J. 75 Antonione C. 20 Antoniu N. K. 61 63 Antonova V. P.,74 Antonovich V. A. 58 Anzai K. 220 Aoi N. 287 Aoki K. 266 Appel R.,80,106,107,108,109 Appelman E. H. 149 Appleton S. L. 237 Apriletti J. W. 337 Arafat A. 39 Arcas A. 295 Archiprete C. 335 Archundia C. 340 Arena G. 283 Arends J. 4 Arewgoda M. 233 Arkhipov S. M. 75 Arkle V. K. 316 Arkles B. 13 Arko A. J. 320 Arlen C. 7 Arlinghaus R. T. 148 Armitage P. D. 163 Armstrong C. 327 Armstrong D. R. 19 Armstrong J. E. 256 Armstrong R. L. 301 Armstrong R. S. 262 Armstrong W. H. 213 224 Amaudet L.8 Amaud-Neu F. 316 Amdt V. 110 Arnold A. P. 302 Amold D. E. J. 124 156 Amold S. E. J. 108 alahti S.,283 Zzabalaga P.,282 Arsenault L. J. 339 Artigao M. 295 Aruffo A. A. 127 229 Asadov M. M. 76 Asakura Y.,327 Asatryan R. S. 338 Asch L. 318 Ashe A. J. 114 Ashida Y.,169 Ashtdn H. C. 226 Aslanov L. A. 165 Aspinall H. C. 207 Asplund M. 275 276 Astfalk Ch. 333 Astheimer L. 341 Astheimer R. J. 47 Astruc D. 202 229 Atanosov M.A.. 281 Atha P. M. 197 Atkins R. M. 309 Atwood J. L. 9 42 66 70 91 104 173 184 23 1 259 260 Aubke F. 168 Auburn M. J. 95 Audisio G. 112 Auk B. S. 153 158 Autenrieth D. 205 Averbuch-Pouchot M. T. 289 296 Averill B. A.194 225 Avila M. J. 328 Avrorin V. V. 325 Awang M. R. 200 Awang R. A. 292 Aygen S. 80 Aymonino P. J. 186 Ayoub P. M.,338 ham K. A. 269 Azhipa L. T. 341 Azman S. N. 292 Azuma Y.,99 Azumo N. 281 315 Babaera P. K. 71 Baban J. A. 35 Babanly M. B. 76 Babcock G. T. 241 Babcuck L. 24 Babel D. 278 Bachechi F. 263 270 Bachmann K.,62 Backvall J. E. 266 Badtiev E. B. 167 Baenziger N. C. 127 128 187 224 297 Baerends E. J. 228 Biizold D. 276 Bagieu-Beucher A. D. et M. 296 Bagnall K.W. 323 324 325 Bahs H. J. 309 Bailey N. A. 12 129 186 192 202 248 284 297 Bailey P. M. 263 Bailey S. R. 159 Bailey W. J. jun. 301 Bain A. D. 202 Bairamashvili I. A. 19 Baird D.M. 189 Baird M. C. 261 Bakac A. 118 Baker R. T. 53 262 Bakhmutov V. I. 285 Balahura R. J. 238 Balashevskii G. F. 313 Balasubramanian P. M. 238 Balch A. L. 219 261 269 Bald L. 276 Baldar J. 335 Baldwin R M. 337 Balhura R. A. 239 Ball J. 310 Ballestracci R. 3 I5 Balliston G. A. 323 Ballivet-Tkatchenko D. 186 Balogh-Hergovich E. 275 Balschi J. A. 316 Balt S. 238 239 Balzani V. 237 Banci L. 281 Bancroft G. M. 147 295 Bandini A. L. 270 Banditelli G. 270 Bandyopadhyay P. 189 Banerjee P. 235 Banister A. J. 103 119 158 Banks E. 226 Bansemer R. L. 180 Bantjes A. 333 Baptista Z. N. R. 343 Baranowski J. 286 Baraw M. 256 Barbier J.-P. 286 Barbieri R.100 Barbul-Rusu A. 115 Barclay S. J. 237 Bard A. J. 229 286 Barder T. J. 206 Bardin V. V. 144 Bardy A. 336 Baret P. 292 Barker G. K.,51 56 271 294 Barkigia K. M. 17 Barley M. 251 Barli P.-L. 249 Barnard P. W. C. 285 Barnes A. J. 148 Barnes C. L. 93 LOO Barnes J. C. 279 Barnes J. W.,327 328 Barnett B. L. 204 Barnov V. A. 338 Barnum D. W. 211 Baron J. C. 332 Ban R. D. 199 260 Barrera H. 296 Barrio J. R. 331 Bamola A. M. 38 Barron P. F. 96 Barrow M. 289 Barry J. 166 Bart J. C. J. 140 I74 Bartel K. 275 Bartell L. S. 161 Barth J. 3 13 Barth V. 108 Barthelemy E. 314 Bartholin H. 314 Bartlett N. 81 167 168 Bartnik R.,296 Barton R. J. 323 Barton T.J. 85 86 Bartsch R. A. 268 Bartsch R. 13 Basato M.,281 284 297 Base K. 39 50 Bashilov V. V. 266 302 Basmadjian G. P. 334 336 Author Index Bastos M. A. V. 330 Bastow T. J. 75 Basu B. 294 Batail P. 134 Bateman L. W. 243 246 292 Bats J. W. 123 296 297 299 Batschelet W. H. 217 218 Batson-Cunningham R. L. Battaglia L. P. 114 281 Battezzati L.,20 Battioni J.-P. 221 Battioni P. 219 Battistuzzi R. 297 Battle P.,212 Bau R. 300 Baudler M. 92 109 110 Bauer H. 89 Bauer V. J. 298 Baumann F. E. 201 Baumgartner E. 21 1 263 Baumrneister U. 107 Bauschlicher C. W. 101 Baussart H. 319 Bautista D. V.,283 Baxter J. D. 337 Baxter S. G. 107 229 Bazan C. 320 Beach D.B. 226 Beachley 0. T. 70 Beagley B. 203 Beak H. K. 283 Bear J. L. 250 Beardwood P. 122 224 Beattie I. R. 149 167 310 Beattie J. K. 242 262 Beattie W.-H. 146 Beauchamp A. L.,99 233 275 289 Beaudry B. J. 305 Beaudry J. 309 Beaulieu W. B. 264 Bechgaard K. 137 Beck W. 22 275 Becker D. S. 298 Becker G. 106 186 260 Becker J. Y. 251 Beckerdite J. M. 147 Beckett M. A. 40,46 271 Bedell S. A. 237 Bednarczyk E. 318 329 Beeken R. B. 306 Beerkovitch-Yellin Z. 241 Beerling-Van der Molen H. D. 332 Begbie C. M. 237 Beguin F. 81 Begun G. M. 322 Behling T. 256 Behm H. 23,24,98,280 301 Behnken P. E. 55 262 Behr J.-P. !.5 Bek&o@u O. 281 Bekk P. 340 Beletskaya I.P.,59 Belford R. L. 154 Belikov V. M. 285 Belin C. 70 Belinskii M.I. 212 Belknap K. 227 Bell L. U. 93 Bell M. J. 302 Bell N. A. 11 43 297 300 Bellitto C. 133 274 Belluco U. 281 Bellugi L. 35 Belrnore K.A. 231 Belokon Yu. N. 285 Bel’skii V. K.,61 Beltran-Porter D. 283 297 Belyakova Z. V. 56 Bencini A. 234 235 279 281 Bencarme C. S. 219 Bencze L. 187 Bender R. 266 Bender U. 193 Benedict J. J. 237 Benedict M. 326 Benedict U. 3 18 Benelli C. 234 235 Benetollo F. 323 324 Benfaremo N. 134 Ben-Hur E. 337 Benjamin T. M. 326 Benn R. 65 Bennett L. E. 216 Bennett M. A. 249 Benoit A. 243 246 Bentley G. E. 327 328 334 Bentsen J. G. 237 Benyhe S.330 Benzel M. A. 148 Beoka-Bets D. 288 Berei K. 341 Bereman R. D. 189 287 Berg J. M. 284 Berg R. W. 68 Berger A. S. 63 Berger G. 331 332 Berger H.-O. 33 Berger R. 335 Berget G. 331 Bergman A. 163 Bergman R. G. 233 234 242 265 Bergstrom D. G. 332 Berkowitz J. 167 310 Bernal I. 22 227 Bernard L. 321 Bernard M. 280 Bernarducci E. 283 Berndt A. 20 Bernstein E. R. 162 Bero M. A. 285 Bemdge M. 332 Berry F. J. 140 Berry J. 132 256 Berry J. A, 318 Bertini I. 287 288 Bertleff W. 267 Bertram W. W. 73 130 Bessergenev W. G. 308 Best S. P. 262 Bethune D. S.,150 Bett R. 329 Beyer G.-J. 144 337 Bezer M.,288 Bhaduri S. 246 Bhagwat D. A.340 Bhalla A. S.,69 Bharadwaj P. K.,283 Bhatia S. C. 150 Bhattacharjie M. N. 281 Bhattacharya P. K. 329 Bhattacharya S. N. 268 Bhattacharyya A. A. 248 Bhave R. N. 339 Bhoon Y. K.,282 Bianchini C. 41 129 236 240 277 Bibber W. 93 Bickelhaupt F. 98 172 Bielefeldt D. 134 159 Bienert M. 330 Bierbaum V. M.,107 Biernat J. F. 281 285 Bigler R. E. 327 332 Bigoli F. 137 138 223 287 299 Billard C. 101 Billon A. 342 Billups W. E. 4 79 Binamira-Soriaga E. 262 Binder F. 278 Biondi C. 35 Biradar N. S. 284 Birajdar R. S. 341 Birchall T. 114 144 Birdy R. B. 296 Birkel I. 318 Bischof R. 308 Bishop K. T. 329 Bismondo A. 322 Bistram S. A. 191 Bitar H. 29 Bjergbakke E.217 Bjermm N. J. 68 Blachnik R. 140 150 275 Blair L. K. 144 Blake A. 117 140 319 320 Blank T. 298 Blaser D. 32 Blaskie M. W. 277 Blasse G. 165 310 Blesa M. A. 211 Blessing G. 328 Bliefert C. 77 Block F. R. 309 Blosl S. 115 Blondeel G. 315 Blotcky A. J. 339 Bo P. 342 Boag N.-M. 266,271 Boardman A. 296 Boa M. H.,168 Boca R. 278 Bochmann M. 34 Bocian D. F. 222 Bock H. 80 Bodak 0. I. 306 Boden N. 321 Bodenstein D. 114 Bodini M. E. 297 Bodner T. W. 232 Bogge H. 186 192 194,291 Boehm H. P. 81 Bohm M. C. 109 209 Boese R. 26 29 32 Boeuf A. 319 Boeyens J. C. A. 130 240 Bogatskij A. V. 329 Bogdanovic B. 5 Bogge H. 281 Boggess R.K. 130 203 Boggs J. E. 152 Bogl P. 315 Bagreev V. V. 279 Bohacek L. 330 Bohaty L. 296 Bohm. M. C. 33-34 Bohn H.G. 312 Bohra R. 112 Bois C. 23 24 74 Bo-Li L. 334 Bolinger C. M. 179 Bolland J. 19 Boller H. 76 136 Bologni L. 282 Bombieri G. 284 323 324 Bommer J. C. 41,275 Bonati F. 270 Bond A. M. 201 237 261 273 302 Bondar A. M. 23 Bondarevskij S. I. 343 Bonfichi R. 258 Bonnemann H. 5 Bonner F. T. 102 Bonomo R. P. 283 Bontchev P. R. 187 Boo W. 0.J. 163 175 226 Book L. 300 302 Bor G. 243 Bordas J. 288 Bordignon E. 237 Bordner J. 237 Boree W. M. M. J. 9 Boreham C. J. 172 188 Borer L. 212 Borgi E. 288 Borisenko A. A. 59 Borish E. T.292 Borisov A. P. 43 Borm J. 104 Borsodi A. 330 Bortolini O. 205 Bos W. 292 Bosman W. P. 292 294 Bassard G. E. 201 Bossek U. 206 Bassuyt A. 336 Bottomley F. 242 249 Boucher H. A. 239 273 Bougeard P. 202 245 Bougharouat N. 332 Bougon R. 147 162 Bould J. 45 265 Boulon G. 310 Bour J. J. 292 294 Bourges J. Y.,322 Bourne P. E. 296 Boutet J. 330 Bowen P. 168 Bowers M. L. 30 Bowmaker G. A. 277 Boxhoorn G. 96 Boy P. 314 Boyar E. B. 257 Braca G. 261 Brach J. 137 Bracher G. 270 Bracher S. 110 Bradley D. C. 178 185 191 Braga D. 254 258 259 289 292 Braghirolli A. M.S. 329 330 Brand J. C. 35 Braterman P. S. 250 Bratsch S. G. 307 Bratt S. W. 230 Brauman J.I. 219 220 Braun D. J. 314 Braun H. F. 66 314 315 Braunschwig B. S. 234 Braunstein P. 266 Bray R. G. 322 Braydich M. D. 235 Brec R. 124 Breen M. J. 263 Breen P. J. 315 Bregadze V. I. 48 59 Brehm A. 114 Breitinger D. K. 301 Brekhovskikh M. N. 75 Bremard C. 186 Bremner I. 193 Breneman G. L. 278 Brennan D. C. 34 Brenner D. 204 Breslow R. 229 Bret J.-M. 275 Brett M. E. 140 Breunig H. J. 114 Brevard C. 183 245 Brewer G. A. 49 181 235 Brewer W. D. 3 12 Breza M.,278 Brians6 J. L. 100 297 Briant C. E. 132 267 289 292 Author Index Briehl H. 106 Bright R. P. 112 Brill T. B. 234 Brinkman G. A. 338 339 340 Brinkmann R. 5 Brint P.,37 Bristow D.J. 147 Brito K. K. 130 282 Brittain H. G. 315 317 Brixner L. H. 31 1 Broach R. W. 43 Broadley K. 232 Brock C. P. 144 Brockner W. 125 Brodersen K. 11 301 Brodie A. M. 212 287 Brook A. G. 84 Brookhart M. 231 232 Brooks M. S. S. 320 Brooks W. V. F. 123 159 249 Broomhead J. A. 188 Browett W. R. 222 Brown C. 28 Brown D. 318 323 324 325 Brown F. C. 358 Brown G. M. 250 Brown H. C. 21 24 Brown H. F. 306 Brown I. 337 Brown J. M. 261 Brown K. L. 212 Brown M. P. 269 Brown P. L. 3 307 321 Brown P. R. 15 Brown R. D. 79 Brown S. J. 107 156 Brown T. L. 232 Brownlee R. T. C. 199 201 Brownstein S. 163 323 Brubaker G. R. 237 238 Bruce M. I. 243 246 290 292 294 Bruder A.H. 172 Brun G. 3 13 Brun P. 243 Brunet-Bilian F. 8 Brunisholz G. 279 Brunner H. 22 194 232 257 Bruno G. 283 284 Bruno J. W. 324 Bruns M. 163 256 Bryan S. J. 27 Bubnov N. N. 154 Buchanan G. W. 302 Bucher E. 314 Bucher J. 342 Buchler J. W. 190 205 Buchmeier W. 98 125 296 Buchner W. 201 Buck A. J. 276 Buckingham D. A. 237 Budinger T. F. 327 331 Budzelaar P. H. M. 20 Buehler J. 22 1 Author Index Burger H. 155 Bues V. W. 125 Buhks E. 211 Bui Huy T. 147 Buisson G. 172 Bukaska-Strzyzewska M. 281 Bukhteev L. N. 70 Bull C. 216 Bulc N. 72 Bulychev B. M. 61 317 Bumiller W. 342 Bunce L. A. 329 Burford N. 120 Burg A. B. 107 157 Burger K.21 I Burges K. 292 Burgess K. 253 292 Burgi H.-B. 289 Burk J. H. 128 Burkett H. D. 203 Burkhardt E. W. 260 Burlet P. 314 Burlitch J. M. 128 Burnasheva V. V. 67 Burnett R. S. 326 Bums G. T. 85 86 Bums J. H. 323 Bums R. C. 162 265 Burow M. 132 Burriel R.,281 Burschka Ch. 201 Bursey M. M. 102 Bursten B. E. 252 Busch D. 286 Busch D. H. 216 241 Busch J. M. 235 Busch K. L. 291 Busetto L. 128 243 253 Bushman D. R. 288 Buslaev Yu. A. 144 146 307 Busnot A. 280 Busnot F. 280 Busquet G. 336 Buswell J. T. 319 Butcher R. J. 235 237 Butler I. S. 181 Butler N. E. 235 Butler T. A. 337 Butler W. M. 190 Butman L. A. 50 Bym M. P. 222 Bzenic J.335 Cabani S. 118 Cabeza J. A. 292 Cabicar J. 326 Cacace F. 330 338 Caciuffa R. 319 Cadee M. C. 71 Cadogan J. I. G. 110 Cahill P. 202 Cahoon J. 331 Calabrese G. S. 242 Calebrese J. L. 260 Calage Y. 162 Calderazzo F. 114 180 317 Calhorde M. J. 132 267 Calis G. H. M. 294 Callahan A. P. 336 Callahan P. M. 241 Callahan R. W. 216 Callan B. 291 Calligaro L. 281 Callot H. J. 222 Calogero S. 216 Calvert J. M. 250 Calvert R. L. 229 Camelli M. 289 Camellini M. T. 246 302 Camenzind M. J. 205 Cameron J. H. 216 Cameron T. S. 95 Carniniti R. 3 15 Camp E. 319 Campbell E. J. 148 Campbell G. 166 318 Campbell J. C. 187 Campelo J. M. 68 Campuzano C. 343 Camus A.277 Canadell E. 234 Cannas M. 274 Canning L. R. 261 Cannon J. F. 19 Cano C.-H. 292 Cano M. 300 Canter N. 38 Canti E. 288 Canty A. J. 302 Capelli B. 233 CapitaLVallvey L. F. 297 Cardin C. J. 97 201 Cardin D. J. 97 201 Cariati F. 140 278 287 296 Carlin R. L. 281 Carlowitz M.V. 152 Carlsen L. 342 Carlson C. W. 94 Carlson K. E. 334 Carmona E. 184 Carniero K. 274 Carr A. M. 237 Carr A. W. 101 Carr S. W. 201 Carrano C. J. 112 215 216 Carre D. 73 Camedo G. A. 200 292 Camllo-Cabrera W. 276 Carty A. J. 228 243 248 289 302 Caruso F. 289 CasabB J. 297 Casalnuovo A. L. 292 Casella L. 283 284 288 Casella V. R.,329 Cascllato V. 323 Caserin M.240 Casey C. P. 175 Casey J. B. 36 Caspar J. V. 250 Cassel J. 239 Cassol A. 317 322 Castan P. 275 282 Castel A. 89 Castiglioni M. 338 Casy C. P. 230 Catinat J.-P. 274 Catsimpoolas N. 336 Caudill H. H. 329 Caulton K. G. 180 276 Cava M. P. 134 Cavell R. G. 107 110 155 156 Cayret C. 249 Ceccanti N. 118 Ceccarelli C. 212 282 284 Cecconi F. 243 264 302 Celeda J. 3 Celustka B. 71 Ceriotti A. 243 259 Cernik V. 326 Cerny R. L. 102 Cesbron F. 280 Chabot B. 66 Chachaty C. 322 Chadhu G. K. 299 Chadwick D.-L. 220 Chagas A. P. 296 Chakravarty A. R. 250 Chakravorly R. 108 Chakravorty A. 189 250 286 Chamma D. F. S. 330 Chan L. T. 127 224 Chan T.C. S. 295 Chance K. V. 149 Chandhuri M. K. 281 Chandrasekharan J. 5 21 Chang C. K. 241 Chang C. T. 317 Chang D. 250 Chang J. C. 187 Chang S. C. 80 154 Chang Y. M. 84 Chapman S. K. 288 Chappel S. D. 271 Chapuis G. 279 296 Charles N. G. 299 Charpin P. 320 Chaska J. 333 Chatani N. 232 Chatgillaloglu C. 154 Chatt J. 184 188 Chattopadhyay T. K. 301 Chaudhari S. K. 68 Chaudhary S. K. 299 Chaudhuri M. K. 214 Chaudhury M. 191 Chaudret B. 249 Chaughule R. S. 315 Chaumette P. 176 Chauternps P. 292 Che C. M. 264 272 Checkernikov V. I. 319 Cheema H. S. 214 Cheetham A. K. 212 Cheh C. H. 342 Chelakov A. K. 154 Chemla M. 169 Chemyak A. I. 62 Chen C.K. 243 Chen L.-H. 144 Chen P. 31 1 Chen T. 35 Chen Y. 31 1 Chen Y. S. 227 Cheng C. H. 243 Cheng R.-J. 219 Cheng Shen 317 Chermann J.-L. 183 Chernaya N. G. 22 Chernyshev E. A. 56 Chernysheva V. F. 299 Cheshnitskii S. M. 67 Cheskey P. T. 243 Chester N. 33 Chetuiti M. J. 101 196 Chevalier B. 20 315 Chevallier P. 162 Chevrier B. 190 Chew V. S. 342 Chianelli R. 132 Chiari B. 213 280 Chiaroni A. 221 Chicote M.T. 293 295 Chieh C. 302 Chien J. C. W. 219 Chiesi-Villa A. 130 173 207 276 290 293 Chikara M. 236 Chikazumi S. 312 Chilingarov N. S. 162 Chini P. 243 258 Chinn J. W. 234 Chinn J. W. jun. 3 Chipania N. N. 154 Chirakal R. 333 Chisholm M.H. 101 195 196 197 198 Chiu H. T. 101 196 Chiu K. W. 243 Chiu T. L. 317 Chivers T. 113 120 121 122 Chmutova M. K. 342 Choon 0.C. 17 Choppin G. R. 316 321 325 Chopra S. 242 Chottard G. 222 Chottard J.-C. 221 Chou M. H. 234 Choudhary V. R.,68 Choudhury S. 301 Christe K. O. 22 102 140 145 147 148 149 154 155 Christensen J. J. 15 Christie K. O. 80 Christoph G. G. 216 Christoffersen J. 4 Christoffersen M. R. 4 Christou G. 127 177 195 225 Chuang I. S. 43 Chung C. S. 285 Chung D. D. L. 168 Church S. P. 207 Churchill M. R. 70 201 Ciabrini J.-P. 184 Ciampolini M. 236 Ciani C. 287 Ciani G. 204 251 258 259 296 Ciavatta L. 322 Cifka J. 335 336 Ciliberto E.324 Cimetiere C. 328 Cingi M. B. 279 283 Cini R. 235 Cinquantini A. 235 Cipollini R. 338 Ciriano M. A. 292 Cisarova I. 39 Clampitt K. S. 334 Clark C. G. 321 Clark C. R. 237 Clark G. R. 80 277 Clark H. C. 101 Clark I. E. 22 Clark J. C. 332 Clark J.-H. 107 156 Clark L. D. 321 Clark R. J. H. 129 193 224 274 338 Clark S. F. 251 Clark T. 3 4 5 34 78 Claus F. 155 Clearfield A. 99 237 283 Clegg W. 4 21 80 92 114 119 129 193,237 246 248 276 277 291 292 299 Cleland W. E. 225 Clemetson K. J. 331 Clifford F. 283 Cline S. J. 191 Clive D. L. J. 298 Cloutour C. 336 Co M. S. 212 Coates G. E. 11 Coates J. H. 282 298 Coates R. M. 35 Cocco G. 20 Cocco S.179 186 Cocoran E. W. jun. 38 Coddington P. M. 238 Coelho A. L. 216 Coenen H. H. 337 Coffindaffer T. W. 196 Cohen H. 238 242 Cohen-Added C. 292 Colborn R. E. 246 Colburn C. B. 156 Author Index Cole W. 337 Cole-Hamilton D. J. 69 245 27 1 Coleman R. S. 334 Coles G. S. V. 274 Colin J. 19 Colligiani A. 261 Collingwood J. C. 226 Collins C. H. 326 340 Collins K. E. 326 Collins M. A. 247 Collins R. L. 229 Collins T. J. 219 Collman J. P. 219 220 Colquhoun H. M. 271 Colton R. 101 201 302 Colulli W. J. 13 Comar D. 330 331 332 Comet M. 330 336 Conder H. L. 272 Condorelli C. 167 Conlin R. T. 85 Connelly N. G. 228 232 289 Conrad D. 250 Consiglio G. 251 Constable E.C. 295 300 Constant G. 300 Contant R. 184 Conti G. 118 Conti M. L. 336 Conti P. S. 331 Contreras J. G. 58 Contreras R. 26 Conway P. 226 Cook J. 302 Cook S. L. 248 252 Cooke M. E. 288 Cooks R. G. 291 Coombe V. T. 249 252 Cooper M. K. 229 Cooper J. N. 237 Cooper D. A. 242 Coornaert S. 336 Copia G. 297 Coppens P. 220 222 Corain B. 28 1 284 297 Corbett J. D. 171 31 1 Cordes A. W. 122 173 Corey E. J. 5 Corfield P. W. 282 Cornelisse R. M. 281 Coming J. F. 196 Corradi A.-B. 114 281 Comu R. J. P. 89 Costantini J. M. 117 140 319 Costanzo L. L. 167 Costello C. E. 204 Costes J.-P. 175 284 323 Cot L. 296 Cotton F. A. 163 171 176 177 178 179 197 199 206 207 250 252 272 Coucouvanis D.127 128 188 194 224 225 Author Index Coulon C. 134 Courtney A.-R. 99 Cousson A. 117 140 166 Couston J. W. 351 Coville N. J. 230 Covino J. 132 Coulan D. O. 137 Cowie A. G. 248 292 Cowley A. H. 97 103 104 105 106 107 119 227 229 Cox A. P. 153 Cox K. C. 284 Crabtree G. W. 320 Cragg R. H.,25 28 Cram D. J. 3 Cramer J. A. 339 Cramer R. E. 324 Cramer S. P. 182 Craytor B. C. 288 Creaser I. F. 239 Creaser I. I. 238 Cremers T. L. 319 320 Creswick M. W. 227 Creutz C. 234 235 245 261 Crisp G. T. 271 Crisponi G. 138 Cristiani F. 256 Croft M.,308 Croize J. 330 Cronin J. P. 37 Crook J. E. 45 46 50 265 27 1 Crousier J.20 Crousier J.-P. 20 Crouzel C. 332 Cucca P. 315 Cuillerdier C. 322 Cullen D. L. 112 Cummings S. C. 235 Cuninghame J. G. 329 Cunningham D. 100 Curtis E. C. 145 Curtis M. D. 93 Curtis N. J. 262 Curvetto N. R. 337 Cutforth B. D. 301 Cutler A. R. 232 Cygani A. 285 Cygler M. 227 Cymbaluk T. H. 240 Czech B. 13 Czernuszewicz R. S.,224 Czeska B. 256 Dabeka R. W. 323 Dabosi F. 296 Dahan F. 282 Dahl J. R. 327 331 332 Dahlstrom P. L. 128 185 193 Dahy D. 69 Dakkouri M. 94 Dakternieks D. 101 302 DAlfonso G. 204 Dalvi A. G. I. 165 Damhus T. 237 D’Amico K. L. 296 Damien D. 117 140,319 320 Dammel R. 80 Damoder R. 285 291 Dance I. G. 129 277 282 287 291,299 301 Dance J.-M.164 Dancey K. P. 298 DAndrea A. 315 Daniels R. J. 328 Daniels W. J. 328 Daolio S. 112 Daou J. N. 308 Daoud A. 300 Daporto P.,236 Dapporto P. 264 283 Dartmann M. 113 Dartiguenave M. 233 289 Dartiguenave Y. 233,289 Dash A. C. 64 238 284 Dash B. 284 Datta D. 286 Davan T. 38 Dave S. M. 327 Davidov D. 81 168 Davidson G. 61 Davidson J. L. 202 241 Davidson K. 202 Davies A. G. 99 Davies D. L. 246 Davies G. 276 Davies J. A. 101 268 295 Davies K. M. 278 Davies S. G. 229 249 Davis J. 331 Davison A. 204 334 335 Davydov Yu. P. 321 Dawkins G. M. 175,228 243 Dawoodi Z. 254 Day M. C. 66 Day R. O. 99 110 113 Day V. W.324 De A. 329 Deacon G. B. 302 Deal W. R. 3 18 Dean P. A. W. 300 de Andrade J. C. 326 DeArmond M. K. 217 Debnath N. C. 21 1 Debreczeni F. 187 280 282 de Britto J. L. O. 330 De Brosee C. W. 263 de Brosse C. W. 9 Debroy A. 281 DeCian A. 190 Decinti A. 297 de Clerq P. 331 Dedgaonkar V. G. 339 340 Dee T. D. 300 Deeming A. J. 207 DeFotis G. C. 225 de Franco N. 177 186 37 1 Deganello G. 249 de Graff R. A. G. 218 Degun S. 328 Dehnicke IC 155 165 178 186,204 256 Deits T. L. 298 de Jersey J. 214 de Jesus E. 75 De Jesus 0.J. 327 de Jong F. 14 334 340 De Keuser Th. 68 de Keyzer G. C. M. 300 De Kock R. L. 37 44 228 230 Delacote I?. 314 de la Fuente K.288 de la Torre J. 340 Del Fiore G. 332 Delhaes P. 134 Delhez R. 68 Deljac A. 284 Dell’Amico D. B. 317 Del Paggio A. A. 277 Del Pino C. 302 Delpy K. 28 Del Zotto A. 284 Demartin E. 128 243 278 Demazeau G. 164 Dembovskii S. A. 75 DeMember J. R. 291 Demertzi D. 297 De Meyer M. 144 Demidov V. N. 143 de Miguel A. V. 263 De Munno G. 283 Dence C. S. 331 Deneufville J. P. 152 Denisov A. F. 329 Dennis G. R. 229 de Novion C. H. 117 140 319 Denti G. 186 192 264 283 de Oliveira 0. A. 296 De Pape R. 162 Deplano P. 137 138 223 DePuy C. H. 107 de Ropp J. S. 219 D’Errico J. J. 93 Desbat B. 147 Deschler U. 8 107 Deshmukh P. 44,230 Deshpande S. V. 287 de Silva A.G. 330 DesMarteau D. D. 80 149 154 Despande S. V. 288 Deutsch E. 204 237 238 Deva M. M. 237 De Vere T. C. 68 Devillanova F. A, 256 Devilliers D. 169 Devina 0. A. 321 Devyatkina E. T. 63 Dewey C. G. 180 De Young D. J. 83 de Zeeuw R. A. 330 Diaddario L. L. 286 Diaddario L. L. jun. 282 Diamantis A. A. 251 Diaz A. 256 Di Bernado P. 317,322 Dickinson L. C. 219 Dickman M. H. 237 280 Dickson M. K. 272 Dieck H. T. 276 Diel B. N. 94 Dienstbach F. 62 Dieter Fischer R. 323 Diksic M. 149 332 Dillen J. 203 301 Dillon K. B. 117 156 295 Dilworth J. R. 3 128 185 187 188 190 193 Dines T. J. 129 193 224 Dirk C. W. 94 Dirksen G. J. 165 Dischino D.D. 334 Di Vaira M. 11 1 124 260 Dixneuf P. H. 243 246 Dixon N. E. 239 262 Do. Y. 179 224 Doadrio A. 188 Doadrio A. L. 192 Doadrio Lopez A. 192 Dock A.-C. 15 Dockal E. R. 282 Dockum B. W. 130 234 Doddridge B. G. 282 Dodgen H.W. 133,242 Doe H. 296 Doedens R. J. 237 280 Doeff M. M. C. 220 Dolcetti G. 264 Dolganev V. P. 22 Dolobel R. 319 Dolphin D. 251 298 Domaille P. J. 183 Domazetis G. 251 Demenech V. 11 Domerle R. 163 165 Dong Vu. 145 Dongre V. G. 299 Doniach S. 212 Dorfman J. R. 177 287 Dori Z. 182 Dory T. S. 100 Douglade J. 115 Dove M. T. 161 Dowling N. I. 271 Doxsee K. M.,219 Doyle G. 276 D' Parish R. V. 291 Draganjac M. 127 188 224 Drane A.S. 129 186 Draux M.,22 Dreher C. 190 205 Drenth B. F. H. 330 Drevenkar V. 284 Drew M. G. B. 12 117 165 176 277 285 Dreyer I. 144 335 337 Dreyer R. 144 335 337 Drioli P. L. 235 Drobyshevskii Yu. V. 162 Druzhinskii B. F. 308 Dubois F. 330 Dubois L. H. 241 Dubourg A. 275 Dubrawski J. V. 251 Dubs R. V. 238 Ducassou D. 336 Ducourant B. 151 Dudareva A. G. 3 11 Duke E. 172 Duffy N. 93 Dufour C. 318 Duisenberg A. J. M. 6 12 280 Du Mont W. W. 97 109 114 Dunaj M. 283 Dunbar K. R. 207 Duncan J. A. S. 264 Duncan R.H. 62 Dunnigan D. A. 332 Dupart E. 134 Dupart J.-M. 30 112 Duplatre G. 341 Duprat M. 296 du Preeze J. G. H. 166 Duraf S. A. 163 176 Durand J.296 Durand R. R. 219 Durij A. 289 Dusausoy Y. 266 Dutschka K. 333 Duttaahmed A. 257 Duttara M. R. 263 Dvurechenskaya S. Ya. 56 Dwarakanath K. 239 Dwight K. 132 Dwyer J. P. 327 D'yakov V. M. 154 Dyer A. 338 Dyke A. F. 242 246 Dykstra C. E. 148 Dzelilovic E. 238 Dzhobawa D. Sh. 19 Dziemianowic T. 167 Eaborn C. 6 89 90 107 230 Eakins M. N. 331 Eastwood F. W. 79 Easwaran K. R. K. 17 Eaton G. R. 285 291 Eaton S. S. 285 291 Eberhardt N. L. 337 Ebihara H. 340 Ebihara M. 239 Ebner M. 267 Ebsworth E. A. V.,94 108 157 263 Echegoyen L. 14 Author Index Eckers W. 125 296 Eckert-Maksic M. 109 Eckrich T. M. 5 Edelstein N. 319 Edelskin N. M. 43 172 Edguer E.327 Edlestein N. 342 Edwards B. H. 173 Edwin J. 33 34 Effantin J. M. 314 Efinov M. E. 321 Efremenkov V. M. 321 Eggleston D. S. 278 Egler H. 330 Egorov A. I. 327 Egorov A. M. 61 63 Egorova N. V. 59 Ehrenkaufer R. 330 Ehrhardt G. J. 328 Ehrin E. 331 Eichbichler J. 301 Eichhorn G. L. 63 Eick H. A. 309 310 Eidem P. K. 182 Einstein F. W. B. 95 198 245 253 Eisenberg F. G. 309 Eisenberg R. 265 Eisenhut M. 336 Eisenmann B. 14 138 Eisenstein O. 173 234 Eiserberg R. 284 Eisman G. A. 130 234 Eiswirth M. 31 1 Eklund P. C. 168 Elam W. T. 214 El-Asrag H. 329 El-Bayoumy S. 329 Elbert T. 332 Elcesser W. L. 177 Elder R. C. 237 Elesin A. A, 343 El-Ezaby M.S. 287 El-Gallad T. T. 193 El-Garhy M. 336 Elgavish G. A. 63 El-Hinnawi M. A. 127 227 El Hosary A. A. 61 Elias H. 284 El-Kaddar Y. 89 Eller P. G. 319 320 Ellert 0. G. 279 Ellis C. D. 250 Ellis D. E. 180 241 Ellis J. 3 307 321 Ellis J. E. 180 181 Elmaleh D. R. 333 Elmer P. S. 79 El Mouhtadi M.,29 El Murr N. 186 Elsaer A. 158 El-Sayed M. A. 276 El-Shaboury G. 336 El Stiefel 129 Author Index Elton J. 309 Eltore R. 291 Eltzner W. 186 192 Elze T. W. 307 Emran A. 334 Emri J. 35 Emsley J. 23 Endesfelder A. 246 Endicott J. F. 235 238 286 Endres H. 278 279 282 Engel N. 66 315 Engelen B. 98 125 296 Engelhardt L. M. 181 Engelhardt P.M. 91 Engerito J. S. 11I Englehardt L. M. 9 Engler E. M. 137 Englert U. 180 English D. R. 222 English R. B. 163 243 259 Engst P. 20 Enjalbert R. 164 Enlow P. D. 261 Ennan A. A. 153 Ennett J. P. 249 Enninga 275 Enoki S. 243 Ensinger U. 114 Ensling J. 218 Enwiya B. Y. 225 Enzo S. 20 Epstein P. S. 93 Ercolani G. 14 118 222 Erdik E. 25 Erdman A. A. 56 Erdos P. 317 Eremenko I. L. 279 Eremenko N. K. 302 Eremin V. P. 341 343 Eriksen K. A. 276 Eristavi A. M. 19 Erman J. D. 222 Ermer S. 246 302 Ermolina G. E. 61 Ernst R. D. 209 240 249 Erofeev A. B. 317 Erre L. 287 Emngton R. J. 191 Erwin W. R. 330 EscoSar C. 283 Esha F. S. 12 Esho F.285 Espejel M. B. 337 Espenson J. H. 118 235 238 Espinosa P. 297 Esre L. 140 Estrada T. P. 334 Etienne J. 69 Etourneau J. 20 315 Ettore R. 295 Euler W. B. 193 223 Evain M. 124 Evans E. J. 237 Evans H. F. 291 Evans J. 248 252 253 Evans W. J. 36 Evgen’ev S. B. 73 Ewa K. 309 Ewin G. 9 Exner O. 110 Extine M. W. 163 176 Eyermann C. J. 143 154 Eyring L. 163 306 Ezhov A. I. 311 Ezhov Yu. S. 162 Fabbrizzi L. 242 285 Fabre J. M. 134 Fabretti A. C. 275 Facchini L. 81 Facci J. S. 250 Fackler J. P. 243 Fadeley C. L. I12 Faggiani R. 145 202 Fairlie D. P. 239 Faischi P. 277 Faischi R. 276 Fajer J. 17 Falaleev 0.V. 161 318 Falshaw C. P. 284 Falvello L.R. 177 179 197 207 250 272 Famili A. 173 Fan G. 278 Fan Y. 317 Fanchiang Y.-T., 295 Farah M. Y. 342 Farnath D. A. 237 Farneth W. D. 276 Farnsworth P. B. 19 Farona M. F. 173 Farr J. P. 269 Farrokhzad S. 332 Farrow N. J. 246 Farmgia L. J. 253 292 Farver O. 264 Fasano A. E. 276 Faulkner L. R. 222 Faure R. 296 Faus J. 212 214 Favier J. S. 330 Favre P. 302 Fawaz R. A. 336 Fay R. C. 171 172 173 237 Federov P. P. 31 1 Fedorov V. A. 74 Fedotov M. A. 183 Fee J. A. 216 224 Feher I. 35 Feher M. 92 110 Fehlner T. P. 33 44,230 Feindel W. 332 Feldmann F. N. 250 Feldner K. 167 Felkin H. 229 249 Fender B. E. F. 321 Fenglan Yu. 317 Fenske D.256 Fenton D. E. 12 175 284 323 Ferey G. 162 Fergusson J. E. 165 182 265 Fernandez E. 295 Fernandez M.J. 94 265 Fernandez-Valverde S. 340 341 Ferreira A. M. de C. 216 Ferreiri R. A. 332 Ferren L. A. 336 Fem D. 322 Femeri R. A. 333 Ferro L. J. 339 Figard J. E. 216 Figgins P. E. 318 Figgis B. N. 240 282 Filip J. 330 332 Filipek S. M. 308 Fillebeen-Khan T. 249 Finch A. 117 295 Fink M. J. 82 83 Finn R. D. 327 Firnau G. 146 333 Firouzbakht M.L. 339 Firtear P. 100 Fischer C. 279 Fischer J. 109 176 Fischer K. 312 Fischer P. 308 309 Fischer R. D. 317 Fischer S. 144 Fisher B. L. 112 Fisher D. J. 265 Fisher E. 289 Fitch A. N. 321 Fitzgerald B. J.227 296 Fitzgerald W. 283 Fitzpatrick L. J. 129 287 291 Fitzpatrick P. J. 181 Fjare D. E. 247 Fjare K. L. 180 181 Fjeldberg J. 97 Flahaut J. 69 314 Flamini A. 133,274 Flamman R. 106 Fleischer T. 150 164 Fletcher J. L. 202 Fletcher R.,279 Flint C. D. 320 Flioriani C, 293 Flodstroem A. 313 Flood A. C. 193 Floriani C. 130 173 174 207 276 277 ?90 Florjancyk Z. 64 Flouquet J. 312 Fluck E. 113 Flynn K. M.,104 105 227 Foces-Foces C. 292 Fochi G. 174 Forster H. 165 Foise J. 132 Folcher G. 8 Foley D. P. 284 Foley J. 22 283 Folting K. 194 197 276 Fong A. 252 Font-Albana M. 11 Font-Altaba M. 297 Foosnaes T. 69 Forchion A, 322 Ford J. E. 3 11 Ford P.C. 243 Ford P. D. 197 Forgues A. 227 Formicka-Kozlewska G. 28 8 Forminykh V. I. 341 Fornasini M. L. 66 Forshey P. A. 221 Forsman W. C. 167 Fortier S. 277 Fortman J. J. 235 Fotiev A. A. 67 Fourcade R. 151 Fournier J. M. 319 320 Foust D. F. 254 Fowler D. E. 343 Fowler J. S.,329 333 Fox C. L. jun. 297 Foxman B. M. 237 Foyentin M. 319 Fraenkel G. 6 Fragala I. L. 324 Frances J. M. 132 Francisco R. H. P. 279 Francois B. 8 Francois J.-P. 291 Frange B. 29 Frank A. 34 Frank J. P. 339 Frankel R. B. 225 Franklin K. J. 335 Franz E.-D. 150 Franzen H. F. 135 306 Fraser I. F. 144 Freauff S. 334 Freeman C. M. 237 Freeman M. J. 247 292 Freeman W.A. 25 273 Freiberg L. A. 332 Freiser B. S. 240 Freiser H. 241 282 298 Frejd T. 5 French R. J. 164 182 Frend A. 337 Freni M. 204 Frey T. 284 Friant P. 178 Friedkin M. 333 Friedlander M. V. 134 Friedman A. M.,327 334 Friedt J. M. 310 318 Friesen C. D. 223 Friesen G. D. 39 193 Frijns J. H. G. 13 Frit B. 74 Fritz G. 89 109 Fritzsche U. 291 Frohn H. J. 146 Frolor Yu. L. 154 Fronczek F. R. 13 279 Frost R. L. 96 Fruchart J. M. 184 Frye J. S. 62 Fryzuk M. D. 91 172 Fucaloro A. F. 222 Fuess H. 21 94 123 153 296 297 299 Fuger J. 319 Fujii A. 341 Fujimori A. 313 Fujimoto E. K. 291 Fujimoto M. 190 Fujimura J. 3 13 Fujita H. 326 Fujita K. 326 Fukuhara M.327 Fukushi K. 332 333 Fuller D. J. 37 Fuller K. 50 Fultz W. C. 234 Fulz W. C. 260 Fumagalli A. 258 259 Funahashi S. 216 242 Furin G. G. 144 Furukawa M. 341 Fyfe C. A. 68 96 Gabe E. J. 40 78 111 323 Gable R. W. 115 Gabovich A. M. 313 Gabuda S. P. 144 Gaebell H. C. 164 166 289 Gaetani-Manfredotti A. 277 Gaft Yu. L. 59 Gahan B. 203 Gahan L. R. 238 Gahas A. M. R. 289 Gaines D. F. 38 Gal M. 301 Gal S. 61 Galande A. R. 339 Galas A. M. R. 243 274 Gale R. J. 229 Gallagher M. K. 243 302 Gallaher T. N. 68 Galleazzi G. 216 Gallucci J. 228 Galoshina E. V.,305 Galy J. 74 164 300 Galyashin V. N. 62 Gamache R. E. jun. 277 Gambarotta S. 130 173 207 276 290 293 Gamelkoorn H.J. 238 239 Gamlen P. H. 278 Gamp E. 43 172 Ganage L. I. 70 Gandolfi M. T. 237 Gandow R. D. 13 Gansow D. A. 316 Author Index Gantner E. 325 Gao S. 23 Garaj J. 283 Garber K. 158 Garcia A. 68 Garcia C. 26 Garcia M. P. 56 Garcia-Blanco S. 292 Garcia-F’rieto J. 278 Garcia-Rodriguez A. 3 Card G. L. 158 164 182 Garde R. 342 Gardiner D. J. 217 222 Gardini M. 118 222 Garlaschelli L. 258 Gamer C. D. 129 193 197 237 276 277 Garnett E. S. 146 333 Gartman V. K. 31 1 Gasanov G. Sh. 279 Gaspar P. P. 339 Gasperin M. 166 Gastaldi L. 133 274 Gaswick D. 250 Gatehouse B. M. 67 Gates P. N. 117 295 Gatley S. J. 332 Gatter M. G. 40 Gatteschi D.234 235 279 281 Gatto V. J. 13 Gautley M. 330 Gavarri J. R. 69 Gavrilova G. A. 154 Gaia J. 278 283 Gaio J. J. 283 Geanangel R. A. 27 Gebert W. 206 Geerts R. L. 276 Geiger D. K.,220 Geiger W. E. 34 232 233 289 Geike W. 30 Gel’mbol’dt V. O. 153 Gelroth J. A. 216 Genc N. 282 Gengembre L. 319 Gentley T. M. 85 Geoffroy G. L. 260 263 George C. 85 George T. A. 184 201 George-Taylor M. 150 Georgin P. 17 Gerard A. 314 Gerasimov V. N. 335 Gerber T. I. 166 Gerdom L. E. 187 Gerken F. 313 Gerl J. 307 Gersonde K. 190 Gervais G. 243 Geschneidner K. A. jun. 309 Geurink P. J. A. 6 Gewirth A. 224 Author Index Ghanbari H. A, 333 Ghedini M.264 283 Gheller S. F. 199 Ghemard G. 69 Ghilardi A. 263 Ghilardi C. A. 41 111 129 243,264,277 Ghilardi G. A. 302 Ghosh B. K. 250 Ghosh D. 168 Ghosh P. 189 234 288 Ghosh S. K. 214 327 Giacomello,P. 338 Gibb T. C. 211 214 Gibson J. F. 122 224 Gibson Q. H. 219,220 Gigoo S. S. 339 Gilbert T. M. 265 Giles J. M. R.,36 Giles J. R. M. 35 Gili P. 288 Gilje J. W. 324 Gill J. B. 281 Gill R. S. 85 Gill T. P. 229 Gillespie,R.J. 145 165 301 Gillet G. 219 Gilliland D. L. 336 Gilson D. F. R.,181 Gimarc B. M. 25 118 119 Gimblot J. 319 Gimeno J. 292 Ginderow D. 280 Ginos J. Z. 332 Ginsberg A. P. 132 138 264 Ginzburg A. G. 301 Giral L. 134 Girandeau A.298 Girasolo M. A. 302 Giraudeau A. 322 Girichev G. V. 162 Girolami G. S. 208 209 Giubileo G. 225 Giunchi G. 174 Giusti A. 275 Gladfelter W. L. 247 Gladkov V. E. 62 Gladyshevskii E. I. 306 Glas R. W. 342 Glaser J. 75 Glass R. S. 130 236 282 Glatz J. P. 342 Glavas M. 238 Glavincevski B. 323 Glebov V. A. 318 Gleiter R. 109 209 Gleizes A. 280 Glentworth P. 341 Gleria M. 112 Glick M. 212 Glick M. D. 282 Glidewell C. 35 Glosby A. A. 329 Glowiak T. 279 299 Gobbi G. C. 68 96 Godart C. 312 Godart J. 330 336 Goddard J. P. 99 Godfrey A. F. 242 Godfrey N. R. 51 294 Godfrey P. D. 79 Godot J. M. 331 332 Godovikov N. N. 48 59 Goeckeler W. F. 328 Goeden G.V. 132,256 Goel R. G. 270 275 Goff H. M. 187,222 Goffart J. 319 324 Goggin P. L. 75 266 301 Goin G. 328 Gok R.,327 Gokel G. W. 13 14 Goldberg A. B. 164 Goldberg I. B. 154 Goldsmith S. J. 330 Goldstein C. 286 Goldstein M. 300 Goldstone A. C. 316 Goli D. M. 14 Golic L. 72 Golodova K. G. 322 Golubeva A. V. 61 Golubkov A. V. 312 Gomez G. 181 Gomez M. 265 Goncalves R. M. C. 228 Gong Z. 311 Gonzalez M. S. L. 284 Goodacre A. 234 Goodale J. W. 207 Goodall D. C. 281 Goodell P. D. 309 Gooden R. 93 Goodfellow R. J. 266 271 Goodgame M. 296 Goodman G. L. 167 310 Goodman M. M. 336 Goodwin H. A. 218 Gopalakrishnan J. 67 Gopalakrishnan K. V. 315 Gopalan M.278 Gopalkrishnan K. S. 246 Gorbacheva I. I. 56 Gorbunov A. I. 35 Gordienko S. P. 314 Gordon B. E. 330 Gordon S. 321 Gorelenko Yu. K. 315 Goren Z. 15 Gorgues A. 134 Gorokhov L. N. 166 Goryachenkov S. A, 146 Goryacheva E. G. 329 GosLlvez M. 279 Gosney I. 110 Goswami S. 250 Goto T. 313 Gottschalk A. 329 Gottschalk K. E. 102 Goubitz K. 7 Goudsmit R. J. 253 254 Gould E. S. 238 Gould R. O. 249 Goulon J. 178 Gower S. A, 242 Gowland R. J. 102 Gracey B. P. 248 Gracheva M. A. 338 Gracheva N. V. 319 Grassle U. 294 Gratzel M. 298 Graf E. 322 Graham N. K. 281 Graham W. A. G. 265 Grande K. D. 237 Grandjean F. 314 Grandjean J. 17 Granger P. 245 Grannec J.164 Granozzi G. 240 324 Grant D. M. 82 Grant P. M. 327 328 334 Grant R.B. 117 118 291 Grant S. H. 226 Gratzel M. 315 Gray A. C. 343 Gray G. M. 201 Gray H. B. 182 232,272 Gray L. R.,273 Graybeal J. D. 159 Graziani R.,323 Grdenic D. 301 Greaves G. N. 203 252 Grebenik P. D. 174 Grebinskii S. I. 312 Grecu I. 177 Green D. W. 163 Green J. C. 324 Green J. M. 222 Green M. 51 56 175 199 228,243,246,247,253,260 271 292 294 Green M. L. H. 174 Greenaway A. M. 165 182 Greenaway F. T. 288 Greenblatt J. 14 Greene R. L. 241 Greenwood N. N. 45,46 50 265 271 Gregg M. 8 Gregory N. W. 212 Greissinger D. 114 Grenouilleau P. 124 Grenthe I. 322 Grenz M.97 Greskovich E. J. 309 Grev R. S. 88 Grey I. E. 67 Griend L. V. 107 110 Griffith E. A. H. 299 Griffiths L. 217 222 376 Griller D. 78 Grimes R. N. 43 49 57 181 Grinberg E. E. 22 Grishin Yu. K. 59 Grocott S. L. 251 Grootveld M. C. 295 Gropen O. 133 Gros E. G. 335 Gros J. 337 Gross M. 298 322 Grossel M. C. 269 Grossie D. A. 12 Groth P. 12 13 Grove D. M. 242 270 Groves J. T. 190 205 221 Gruehn R. 150 276 Gruen R. 300 Grundy H. D. 67 Grundy S. E. 284 Grzeszczuk M. 233 Grzeta-Plenkovic B. 71 73 Grzybowski,J. J. 216 Gschneider D. 85 Guan-Lin Q. 338 Guarr T. 211 Guastini C. 130 173 207 276,290,293 Gubanova L. I. 154 Gudel H. C. 212 Gudel H.U. 226 Gul A. 281 Guerney P. J. 282 301 Gueros 1. I. 302 Guerra M. 301 Gutlich P. 218 Guggolz E. 92 Guilard R. 178 Guilhem J. 259 Guillaume B. 321 322 Guillaumont R. 319 Guimerans R. R. 261 269 Guitard A. 289 Guitel J. C. 289 Guittard M. 69 314 Gukathason R. R. 267 Gulliver D. J. 273 Gullotti M. 283 284 288 Gundersen G. 27 108 124 156 Gundlach G. 331 Guo Z. 311 Gupta A. 280 Gupta K. C. 74 Gupta L. C. 314 Gupta M. P. 297 Gupta V. K. 279 Gupta Y. K. 280 Gurak J. A. 3 Gurvis R. 339 Gusarov A. V. 166 Gusev A. I. 56 317 Gutenkunst B. 84 Gutierrez J. M. 68 Gutmann V. 27 Guyer C. E. 337 Gwinn H. R. 329 Gyori B. 35 Haar L. W. 280 Haar A.134 159 Haase M. 92 Haasnoot J. G. 218 277 278 283 300 301 Habash J. 320 Haber M. T. 332 Haddon R. C. 79 Hadenfeldt C. 150 Hadjihadis N. 300 Haen P. 312 Hattich T. 101 Haeuseler H. 130 Haeusler H. 73 Hafez M. B. 342 Hagen K. 102 Hagen K. S. 127 224 225 300 Hagenmuller P. 20 164 315 Hagiwara R. 169 Hagiwara S. 327 Hahn F. E. 100 Hahn J. 109 110 Hahn J. E. 284 Hahn P. B. 329 Hahn R. L. 321 Haider S. K. 288 Haiduc I. 115 Haigh P. 284 Haines R. J. 243 259 Haire R. G. 166 318 319 Halfpenny J. 27 Hall J. H. jun. 150 Hall K. P. 292 Hall M. 114 156 Hall M. B. 195 234 243 Hall S. R. 251 Hallaba E. 329 Haller K. J. 82 220 Hallock R.B. 70 Halstead T. K. 321 Haltiwanger R. C. 182 Hamada Y. 86 Hambley T. W. 199 243 Hambright P. 298 Hamburg A. W. 286 Hammer B. 22 232 Hamon J. R. 202 229 Hampl R. 330 Han S. 272 Hanaki A. 298 Hanck K. W. 217 Hancock R. D. 130 240 285 Hand V. C. 102 149 Handel T. M. 237 Hank K. W. 302 Hankey D. R. 253 260 Hansen J. J. 279 Hanser A. 307 Hanson R. N. 336 Author Index Hansson O.,203 Harada T. 280 Haraguchi K. 282 Hardcastle K. I. 246 302 Harding M. M. 263 Hare J. 224 Hargittai I. 77 88 Harkaway S. A. 242 Harlow R. L. 191 276 Harmalker S. 287 Harms T. 331 Harper J. R. 342 Harper P. 327 Harriman A. 250 Harris F. L. 298 Harris J. 279 Harris P.J. 112 Harris R. K. 108 Harris W. R. 216 Harrison B. A. 298 Harrison J. F. 305 Harrison P. G. 87 98 99 100 Harrison W. D. 141 Harrowfield J. M. 237 Harrowfield,J. McB. 72 261 323 Hart F. A. 323 Hart S. M. 130 240 Hartl A. 107 Hartl H. 161 291 Hartl M. 140 Hartley F. R. 268 Hartman J. S 68 96 Hartmann G. 159 207 Hartmann H. J. 288 Hartstock F. W. 283 Hartung E. 23 Harvey D. A. 112 Harwig J. F. 333 335 Hasegawa K. 190 Hasek J. 52 Haselden D. A. 68 Hassan I. 67 Hasse W. 284 Hassen H. A. 337 Hassige R. 6 Hatano K. 220 Hatano M. 171 235 299 Hatfield W. E. 278 280 286 Hathaway B. 22 283 Hathaway B. J. 201 275 282 283 Haubold W. 20 Hauck J.308 Hauert R. 320 Haug H. O. 325 Hauge R. H. 4 79 Haumaier L. 129 Hauptman Z. V. 103 119 Haussiihl S. 296 Hawkins C. J. 237 Hawkins R. T. 15 Hawley M. D. 103 Author Index Hawling W. M. 267 Hawthorne M. F. 52 53 54 55 262 Hawthorne S. L. 172 Hayes J. C. 277 285 Hayes R. G. 220 298 Haylett B. J. 97 Haymore B. L. 132 191 235 256 Hazel N. J. 174 Hazell A. C. 264 Hazell R. G. 264 He D. W. 5 Healy M. A. 97 98 Healy P. C. 275 Heath G. A. 163 249 250 252 Heaton B. T. 243 258 259 289 Hebecker Ch. 150 Hebre W. J. 88 Hecht C. 95 Hedberg K. 102 155 164 182 Hedberg L. 102 155 164 182 Hedrich M. 291 Heeg M. J. 266 Hegarty A. F. 78 Hegde S.35 Heger G. 4 Heide K. 23 Heiman D. F. 334 Heimer N. E. 163 175 Heintz V. J. 25 Heistand R.H. 215 Helber J. 146 Helius F. 337 Hellmann J. 109 Hellmann W. 193 Helm L. 317 Helus F. 331 Hendrickson A. R. 237 Hendrickson D. N. 214 222 285 Hendrickson W. A, 212 Hengesbach J. 34 Henkel G. 177 Henkie Z. 320 Henle H. 159 Hennig H. 276 Henrick K. 254 Hensen K. 21 94 153 Henty M. S. 278 Heppert J. A. 38 Herberg S. 157 Herberhold M. 129 141 175 Herberich G. E. 34 Herbert I. R. 266 Herbranson D. E. 103 Herbstein F. H. 272 Herdtweck E. 162 Herlt A. J. 261 Hermanek. S.. 49 Hernann S. 165 Hermansson K. 63 Hermasson K. 4 Hernann W. A.260 Herndon J. W. 227 Herndon W. C. 36 Herrick C. C. 319 Herrick R. S. 189 Herrmann W. A. 95 106 191 Herron N. 216 286 Hersh W. H. 234 Herskovitz T. 260 Hertz M. R. 318 HervC G. 183 Hervt M. 183 Hess H. 288 Hessner B. 253 271 Hester R. E. 299 Hey E. 165 178 186 Hey R. G. 158 Heyduk E. 281 Heyns A. M. 163 Hiatt M. H. 329 Hietkamp S. 268 Higashi I. 19 66 Higashi J. M. 240 Higashi K. 326 Higgens S. J. 242 Higgins S. J. 262 Higuchi T. 84 103 109 125 Hihara T. 313 Hii P. S. 144 Hildreth R.,299 Hildrith R. 219 Hill C. L. 30 205 Hill D. T. 294 Hill J. D. 9 Hill R. H. 269 Hill W. E. 58 156 203 268 Hiller W. 294 Hillhouse G. L. 191 Hillier I.H. 197 Hilrner W. 23 Himmel S. 105 Himpsel F. J. 319 Hinds J. L. 221 Hines V. L. 286 Hinks D. G. 313 Hinrichs W. 317 Hirai H. 62 Hiraoka K. 313 Hirotsu K. 84 103 109 125 Hirotsu T. 341 Hisajima K. 326 Hitam R. B. 227 Hitchcock P. B. 6 90 97 Hitchcock P. W. 241 Hitchrr,an M. A. 297 Hluchy H. 92 Ho W. C. 290 Hobart D. E. 322 Hobson R. J. 176 Hochheimer. H. D.. 314 Hodges J. A. 314 Hodgson D. J. 191 278 286 Hodgson K. O. 212 284 Hodorowicz S. A. 309 310 Hoechst A. G. 328 Hohn M. 219 Horlein R. 95 Hoeschele J. D. 337 Hoeve W. 327 Hoffman B. M. 193 221 223,241 Hoffman D. M. 33 197 Hoffman T. 335 Hoffmann I. 335 Hoffmann M. R. 88 Hoffmann R.,33,182 Hofmann H.125 Hogenkamp D. J. 276 Hohne G. 41 Hohner U. 29 Holah D. G. 41 Holden N. E. 307 Holland G. F. 180 Holland P. R. 245 Holland R. F. 146 Hollander F. J. 205 Holliday A. K. 69 Hollinger G. 319 Hollis L. S. 272 Holloway J. H. 164 318 Holm R. H. 126 127 177 179 194 195 224 225 300 Holmberg B. 289 Holmes J. M. 110 Holmes R. A. 335 Holmes R. R. 99 110 113 Holrnes-Smith R. D. 95 Holten J. D. tert. 339 Holtman D. A. 225 Holtzberg F. 312 Holwerda R. A. 283 Holz K. 115 151 Holzberg F. 312 Honda S. 187 Hooley J. G. 168 Hoots J. E. 264 Hope H. 5 9 97 104 227 Hoppe K. D. 109 Hoppe R.,150 163 164 165 166 167 276 289 Hoppenheit R.,92 160 Hoq M.F. 238 Hor T. S. A. 132 267 289 Horak M. 20 Horbaczewski A. 281 Horikashi I. 17 Horiuchi K. 330 333 335 Horlock P. L. 332 Horrocks W. D. jun. 315 316 Horvath C. 315 Horvath I. T. 233 254 Hosain. F.. 334 378 Hoskins B. F. 101 115 Hoskins S. V. 80 Hossain M. B. 100 Houghton R. A, 330 Houle W. 135 Hoults T. M. 337 Hounslow A. M. 282 298 Housecroft C. E. 37,44 230 Hovak I. 114 Hovestreydt E. 315 Hovland A. K. 302 Howard B. 245 Howard C. G. 208 Howard D. K. 22 Howard J. A. 276 292 Howard J. A. K. 199 200 253,260,271,292 Howe A. T. 321 Howell J. A. S. 228 Howell J. M. 134 Howells N. D. 132 267 289 Hoyans J. K. 265 Hozumi Y. 195 Hradilek P.337 Hrebenda J. 330 Hriciga A. 15 Hrnar D. C. 66 Hrong Roang Shen 317 Hruby R. 337 HSU L.-I. 44 HSU W.-L. 44 Hu T. 23 Huang H. N. 227 Huang N. Z. 290 Huang W.-S. 134 Huber F. 100 Hubert S. 319 Hudson A. 174 Hurter S. 151 Hutner G. 104 Huttermann J. 2 19 Huffman J. C. 101 177 180 194 196 197 198 235 276 Hugel R. P. 286 Hughbanks T. 182 Hughes A. N. 41 Hughes D. L. 3 75 Hughes J. W. 130 203 Hughes M. N. 102 Hughs D. L. 235 Hulet E. K. 318 325 Hulliger F. 140 Hulsbergen F. B. 284 Humphrey M. B. 231 Hundeshagen M. 331 332 Hunt J. P. 133 242 Hunter G. 115 Hunter G. M. 108 157 Hunter W. E. 42 70 104 231 259 260 Huntley C. M.94 Huong P. V. 147 Hupp J. J. 216 Hupp J. T. 315 Huppmann P. 140 161 Huray P. G. 318 Hurk G. R. 232 Hurst K. 298 Hursthouse M. B. 99 178 185 191 208 209 243 245 274 288 Hu Shengzhi 323 Husk G. R. 231 Hussain W. 184 Hussein M. A. 238 Hussey C. L. 163 289 Huston E. L. 309 Hutchinson J. 128 187 189 193 Hutchinson J. M. R. 329 Hutchinson J. P. 277 285 Hutter E. 342 Huttner C. 34 105 Huy Dung Nguyen 314 Hvoslef J. 9 Hyde B. G. 313 Hyde J. R. 185 Hyde K. E. 238 Hyde P. J. 326 Hynes M. J. 214 281 Ianovici E. 340 Ibers J. A. 130 220 225 240 241 262 268 314 Ice R. D. 334 336 Ichikawa T. 281 Ichimura A. 238 Ido T. 331 333 Iglesias M. 302 Iglesias R.149 Ihmels K. 180 Iijima K. 28 Ijola D. J. W. 71 Ikoma S. 63 Ikorskii V. N. 56 162 Il’in Yu. N. 23 Illuminati G. 14 Ilsley W. H. 298 Ilunga P. N. W. 286 Ilyushchenko 0. N. 335 Imagawa T. 158 Imai S. 70 Imai T. 24 Imamura T. 190 Imasaka Y. 195 Imoto S. 326 Inabe T. 94 Inagaki T. 9 Inamoto N. 103 109 125 Ingold K. U. 154 Ingri N. 62 Innwenti P.,240 Inokawa S. 65 Inoue H. 126 Inoue M. 215 Inoue O. 333 Inoue T. 242 Author Index Inque T. 94 Ionova G. V. 308 Ireland P. 301 Irgolic K. J. 108 Irie T. 333 Isab A. A. 294 303 Isaev I. D. 74 Isaeva L. S. 302 Isci H. 295 Isenberg W. 80 160 Ishari K. 242 Ishchenko A. A. 144 155 Ishchenko N.N. 70 Ishida T. 215 Ishiguro T. 66 276 Ishihara K. 216 Ishii H. 307 Ishii T. 20 Ishii Y. 333 Ishikawa M. 84 314 Ishikowa Y. 327 Ishiwada K. 301 Ishiwata K. 331 Ishizawa N. 66 276 Ishizu K. 281 287 Isied S. S. 252 Ismail I. M. 273 Isobe K. 263 Issaian H. 328 Ito H. 274 285 Ito K. 211 Ito T. 19 66 274 285 309 Ivanchenko A. F. 327 Ivanov A. A. 155 Ivashinnikov V. T. 67 lvashkevich L. S. 155 Iverson B. L. 219 220 Iwaizumi M. 236 284 Iwamoto J. B. 21 Iwamoto M. 226 Iwata R. 331 333 Iyer R. S. 339 Iyoda J. 84 Izatt R. M. 15 Izatt S. R. 15 Izawa G. 333 Izquierdo A. 339 Izumi A. 169 Jacimovic L. M. 335 Jackels S. C. 216 Jackman L.M. 9 Jackson I. T. 12 Jackson W. G. 237 238 239 Jacob P. 20 Jacobsen C. 137 Jacobsen J. K. 331 Jacobson D. B. 240 Jacquier B. 310 Jager G. 114 Jagner S. 275 276 Jahn W. 317 James B. D. 75 James B. R. 251 260 Author Index 379 Jan D.-Y. 44 Jananovic V. 335 Jandik P. 295 Janes S. R. 286 Janoki A. G. 333 Janoki G. A. 333 Janousek Z. 49 50 Janssen E. 65 Janta R. 30 Janzen A. F. 146 Jaouen G. 202,245 Jarman P. F. 96 Jarvis W. 47 Jasmin C. 183 Jasperse C. P. 37 Jastrzebski J. T. B. H. 7 297 Jaud J. 300 Jaulmes S. 69 71 314 Javet C. 279 Jean Y. C. 241 Jeannin Y. 183 Jeanniot D. 313 Jeffrey J. C. 228 243 258 Jeffs S. E. 75 Jeitschko W.314 Jelfs A. N. de M. 178 Jemmis E. D. 5 Jen K.-Y. 134 Jenden C. M. 310 Jennings J. R. 27 Jensen C. 262 Jensen J. A. 247 Jensen J. B. 289 Jentsch D. 62 289 Jesthi P. K. 25 Jezierska A. 285 Jezierska J. 285 Jezowska-Tizebiatowska B. Jha S. 280 Jha S. K. 297 Jimenez R. 295 Jimenez-Reyes M. 340 Jingchun Wang 309 Jinhua Ma. 311 Jircitano A. J. 285 Job R. 229 Joffrin J. 313 Johannsen B. 335 Johannsen B. A. 335 Johannsen I. 137 Johanson W. R. 320 Johansson G. 289 Johansson L. I. 313 John G. R. 230 Johnson B. C. 237 Johnson B. F. G. 247 248 252 253 254 292 Johnson B. L. 237 Johnson B. M. 164 182 Johnson C. R. 238 Johnson D. 239 Johnson D. A.176 Johnson D. C. 313 314 Johnson D. W. 237 Johnson F. O. 237 Johnson G. L. 147 148 Johnson M. K. 224 Johnson P. C. 328 Johnson R. B. 219 Johnston A. J. 239 Johnston H. S. 149 Johnstone R. A. W. 15 Johri K. K. 149 Jolibois B. 74 Jolly D. 149 Jolly P.W. 271 Jolly,W. L. 143,153,154,226 Jones A. C. 69 Jones A. G. 204 334 335 Jones D. F. 243 246 Jones D. H. 279 Jones D. J. 137 Jones L. H. 161 Jones M. jun. 57 Jones P. 222 342 Jones P. G. 62 114 115 125 289 291 293 295 Jones P. J. 164 Jones P. R. 88 Jones R. A. 90 106 198 259 260 Jones S. C. 331 Jones S. E. 287 Jones S. L. 288 Jones T. 300 Jones T. C. 80 Jones W. 81 168 Jorda J. L. 314 Jordan R.B. 242 Jordan R. F. 175 230 Jordanov J. 172 Jorgensen C. K. 318 Jorgensen J. D. 313 Joshi B. D. 165 Jost K. H. 23 Jostes R. 192 Joubert M. F. 310 Jud J.-M. 266 Jugie G. 164 275 Julien R. 313 Julien-Pouzol M. 314 Julve M. 280 Jumas J. C. 74 Jungk S. J. 13 Juranic N. 237 Jurisson S. S. 237 Jutzi P. 6 33 97 108 Kabachnik M. I. 154 Kabalka G. W. 26 330 334 Kabassanov K. 187 KabeSorG M. 283 Kabuto C. 284 Kacena V. 326 Kada J. 102 Kadish K. M. 220 221 236 250 298 Kaesz H. D. 270 Kafafi 2.A. 4 79 Kafitz W. 204 Kagawa S. 226 Kageyama H. 8 Kagramanov N. D. 88 Kahara M. O. 15 Kahn O. 280 Kai Y. 8 Kaim W. 28,298 Kaindl G. 312 Kaiser E.T. 299 Kakihana H. 329 Kalandadze G. I. 19 Kalatzis G. 177 Kalcher W. 106 260 Kalck P. 132 Kaldis E. 308 Kalinin V. B. 306 Kalinin V. N. 58 Kalinina T. A. 72 Kalinnikov V. T. 279 Kalinowski M. K. 176 Kalkowski G. 312 Kallesbe S. 191 Kallury M. R. 84 Kalvius G. M. 318 Kalygin V. V. 343 Kameda M. 38 Kamigaichi T. 3 13 Kaminskii V. F. 276 301 Kaminskii V. V. 312 Kammerer D. 274 Kampel V. Ts. 59 Kampmann D. 29 Kan Y.,238 Kanatzidis M. G. 127 128 225 Kane-Maguire L. A. P. 230 Kanepe Z. 306 Kaner D. A. 253,292 Kanesato M. 239 Kang S. J. 13 Kannerwurf C. R. 94 Kanno M. 326 Kanters J. A. 12 297 Kapoor R. 145 Kappel M. J. 216 Kappenstein C. 786 Kapsch D.N. 328 Karagiannidis P. 277 Karajagi G. V. 284 Karanfilov E. S. 335 Karasawa T. 331 Karayannis N. M. 177 186 Karazhanova G. I. 327 Kardi F. 14 Karipides A. 297 Karlik S. J. 63 Karlin K. D. 277,285 Karnika de Silva K. G. 141 Karpinas D. M. 19 Karraker D. G. 324 Kartasheva N. A, 329 Karunanithy S. 168 Kasai N. 8 Kasantsev A. V. 58 Kashiki I. 341 Kasida Y. 332 333 Kasina S. 333 335 Kaska W. C. 262 Kaspersen F. M. 330 Kasuya T. 313 Katakis D. 177 Kato I. 278 Kato M.,66 82 276 Katoda N. 238 Katoh S. 341 Katovic V. 235 Katsura T. 211 Katz B. A. 222 Katzenellenbogen J. A. 330 333,334 KauEiE V. 164 Kauermann H. 194 Kaufmann E. 3 78 Kaufmann K.J. 17 Kaul B. B. 188 Kaul H. A. 114 Kausar R. A. 316 Kawaguchi M. 169 Kawakami M. 312 Kawamura T. 243 261 Kazansky L. P. 183 Kazennov B. A. 299 Kazmierczak K. 110 Kear C. M. 163 Keat R. 112 Keder N. L. 222 Keenefick D. 22 283 Kehrer H. 94 Keiderling T. A. 25 Kellawi H. 228 Kellenberger B. 270 Keller H. J. 274 Keller H. L. 98 Kelly D. P. 201 Kelly J. M. 201 Kelly P. J. 320 Kelsall B. J. 148 Kemp R. A. 107 Kendrick A. G. 103 119 Kennard C. H. L. 17 Kennedy J. D. 40 45 46 50 265 271 Kennedy S. D. 276 Kent T. A. 215 Kepert D. L. 37 311 323 Kerth J. 113 Keszler D. A. 314 Kevan L. 281 Kevill D. N. 291 Khairoun S. 164 Khaldoyanidi K.A. 162 Khalifa M. A. 235 Khalilov Kh. S. 59 Khalkin V. A. 144 337 341 Khan M. A. 278 Kharitonov Yu. Ya. 74 Kharlamov V. T. 328 Khattak G. D. 319 Khodakovskii I. L. 321 Khova L. S. 342 Kida S. 280 282 Kido G. 312 Kido H. 298 Kieboom A. P. G. 9 Kikoin K. A. 312 Kikuchi M. 339 Kikuchi T. 284 Kilbourn M. R. 331 333 334 Kilduff J. E. 103 104 105 227 Kim K. 132 Kim K. C. 166 318 Kim S. 252 Kimar K. 235 Kimura E. 235 287 Kimura K. 15 Kimura T. 224 King G. D. 201 King K. 13 246 302 King L. J. 336 King M. M. 298 King P. B. 108 King R. E. 111 53 King T.J. 97 99 201 284 Kinkead S. A. 154 Kinneging A. J. 278 Kinney J. B. 260 Kira M. 85 Kirakosyan G.A. 307 Kirchoff J. R. 277 Kirfel A. 19 23 Kirillova N. I. 56 317 Kirk J. R. 333 Kirpatrick C. C. 198 Kirmse R. 204 Kirsch G. 336 Kirschenbaum L. J. 292 Kiselev Yu. M. 146 167 Kisin A. V. 56 Kistenmacher T. J. 137 Kitaev G. A. 73 Kitagawa S. 281 Kitagawa T. 296 Kitamoto A. 326 Kitamura T. 341 Kitaura K. 233 Kiwi J. 315 Kiyose R. 327 Klahne E. 323 Klaiber F. 140 Klassen H. 276 Klauschenz E. 330 Klautice S. 109 Klebe G. 21 94 153 Klee V. W. 136 Kleeman G. 79 Klein C. L. 278 Klein H. A. 5 Author Index Klein H. F. 7 297 Klein H. O. 114 Klein S. I. 105 267 Kleiner T. 11 Kleinmann I. 332 Klepp K. 76 136 315 Klevtsov P. V. 76 Klevtsova R.F. 76 Kliche G. 73 Kliegel W. 30 31 32 Klimashevskii L. M. 75 Klimenko N. M. 144 Kline C. H. 355 Klingebiel U. 92 Klingelhofer P. 162 Klingert B. 263 Klingstedt T. 5 Klinkora L. A. 311 Klinotova E. 330 Klinowski J. 63 68 96 Klop E. A. 280 Kloster G. 331 333 334 Klumpp G. W. 6 Klusik H. 20 Knable G. L. 149 Knapp F. F. 336 Knapp F. F. jun. 26 Knaus E. E. 337 Knauth H. D. 149 Kniep R. 152 Knierim K. D. 339 Knight L. B. jun. 305 Knittel G. 342 Knobler C. B. 52 53 54 55 262 270 Knoch F. 106 107 108 Knoth W. H. 183 Knox C. V. 12 285 288 Knox S. A. R. 242 246 Knut E. J. 333 Knuuttila H. 280 Knuuttila P. 280 Knyazeva L. K. 56 Knyazova N.A. 74 Kobayashi H. 15 Kobayashi K. 281 Kobayashi T. 333 Kober E. M. 217 Kobets L. V. 320 Koch H. 329 Koch M. H. J. 288 Koch S. A. 223 Kochetkova N. E. 342 Koczon L. M. 184 Kodaka M. 299 Kodama G. 37 38 Kodama M. 235 Kodina G. E. 335 Kohler H. J. 88 Koehler W. C. 307 Koehly G. 322 Koehne J. 311 Konig E. 218 Koplin R. 155 Author Index 38 1 Koh K. K. 327 Kohan J. 187 Kohl F. 33 97 Kohler F. H. 30 Kohlmann T. 276 Kohno Y. 281 Koizumi M. 20 Kojima K. 242 313 Kojima M. 333 334 Kojro 0. Eh. 342 Kok R. A. 195 Kokkes M. W. 226 Kokkon S. C. 277 Kokoszka G. F. 286 Kokunov Y. V. 146 Kolar Z. 333 Kolarik Z. 325 Kolb W. A. 329 Kolenko I. P. 67 Koleva D. P. 339 Kolina J. 332 Kovalevskaya Yu. A. 308 Kovba L.M. 72 Kowalski R. S. Z. 297 Koyama K. 278 Kozhevnikova N. M. 73 KoiiSek J. 283 Kozlov F. N. 73 Kozlowski H. 279 299 Kraft A. 276 Kraft V. A. 135 Kraihanzel C. S. 201 Kramer G. M. 322 Kramer L. S. 284 Kramer M. 330 Kramer V. 73 Krasikova R. N. 325 Krasnov K. S. 162 Kratky Ch. 4 Kraus H.-J.,107 108 125 271 Krause M. J. 245 Kravchenko V. V. 23 Kumada M. 84 Kumar K. 239 286 Kumar N. 166 319 Kumar R. C. 103 158 Kumar S. 128 193 Kumari A. 95 Kumin A. J. 237 Kunii S. 313 Kunze K. L. 219 Kunze U. 101 Kuo C. S. 163 175 Kupferschmidt W. C. 238 Kurbanov T. Kh. 279 Kurenkov N. V. 328 Kurihara O. 327 Kuriya M. M.,280 Kurmoo M. 274 Kuroda R.,273 Kursanov D. N. 301 Kurtanjek M. P. 354 Kurylo M. J. 149 Kolinski R. A. 281 Kolomnikov I. S. 74 Kolsi A. W. 279 Komives J. 61 Komiyama M. 62 Komm R.27 Komormicki A. 101 Kondrat’ev S. N. 23 Kondratov 0. I. 73 Konieczny S. 339 Konig G. 67 Konig T. 14 Konig V. T. 138 Konrad R. 92 Krebs B. 25 113 118 177 Krebs V. B. 136 Kreh R. D. 219 Kreichbaum G. W. 260 Kress W. 301 Kreter P. E. 260 Kretschmer M.,302 Kreuer K. D. 321 Krickemeyer E.,192 Kriechbaum G. W. 106 Krill G. 312 Krischner H.,299 Krishna Km. 297 Krishna R. 84 Kusabayashi S. 22 Kusano H.,226 Kusano Y. 3 Kushch L. A. 276 Kutz N. A. 41 Kutzler F. W. 241 Kuwana T. 221 Kuyavskaya B. Ya. 212 Kuzimina L. G. 301 Kuzina A. F. 335 Kuzina V. A. 75 Kuz’min N. M. 62 Kuznetsov 1. Yu. 50 Kuznetsov N. T. 50 59 319 Konstantatos J. 177 Krishner H.,4 Kuzovkina E. V. 321 Konstants Z. 306 Kontis S. S. 339 Krivokhatskij A. S. 326 Krivosheeva N. D. 56 Kwik W. L. 286 Kynast U. 186 Koob R.D. 85 Kopecky P. 329 Kopicka K. 337 Koppen M. 273 Kopylov V. M. 154 Korablev G. A. 67 Korenstein R. 11 Korf J. 332 Korgul P. 81 168 Korobov M. V. 167 Korpar-Colig B. 301 Korshunov V. N. 308 Krogh-Jespersen K. 283 Krohn K. A. 334 Kronrad L. 337 Kroto H.W. 105 267 Kriiger C. 107 108 155 Kruger C. 6 34 65 125 271 Krupa J. C. 319 Kryuchkov S. V. 335 Kubale J. J. 112 Kubiak M. 279 299 Kucharska-Jansen M. M. 34 Kudo T. 88 Laane J. 145 Laangstroem B. 332 Lacis I. 308 Lacy J. L. 328 Lagow R. J. 3 301 Laguna A. 75 289 291 295 Laguna M. 291 295 Lagunas-Solar M. C. 328 Lahaie P. 137 Laher T. M. 289 Lamanna W. M. 231 Korte L. 152 Kuhn G. 276 La Mar G. N. 219 222 Korva V. M. 319 Korytnaya F. M. 306 Kos A. J. 5 78 Kosenko N. F. 65 Kost M. E. 305 Koster H. 249 Koster R. 32 Kostikas A.127 224 225 Kosulin N. S. 318 Kotsupalo N. P. 63 Kotur B. Ya. 306 Kundig E. P.,202 Kueng M. 320 Kusthardt U. 95 Kuhn G. 135 Kuipers H. J. A. M. 238 239 Kuksis A. 8 Kukushkin Yu. N. 143 Kulakov V. M. 335 Kuleshova D. D. 35 Kulieva N. A. 76 Kulkami P. V. 336 Lamb J. D. 15 Lambert K. 99 Lambert R. M. 117 118 291 Lambrecht R. M. 328 Lambrev V. G. 62 Lamotte D. 332 Lance M. 162 320 Lancon D. 221 Landers A. G. 114 229 Landrik C. R.,302 Landro F. J. 3 Kovacs G. 61 Koval’chuk N. A. 59 Kulkami S. A. 340 Kulshreshtha S. K. 218 Landvatter S. W. 334 Lanfranchi M. 287 299 382 Lanfredi A. M. M. 246 264 277 279 283 Lang G. 219 220 Lang H. 105 Langford C. H. 298 Langhof H. 284 Langley R. 163 Langrick C. R. 269 Langridge-Smith P. R. R. 153 Langry K.C. 218 222 Lankard J. R. 150 Lantelme F. 169 Lanzoni E. 20 Lapierre F. 312 Laplace G. 74 Lappert M. F. 9 42 91 97 174 Lara de Vega O. 341 Larbot A. 296 Larin M. F. 154 Larkworthy L. F. 176 197 Larrazkbal G. 297 Larsen S. 191 Lasch J. G. 97 103 104 107 198 227 Lasocka M. 140 Lassailly Y. 312 Lasser W. 173 Laszlo P. 17 Latos-Grazynski L. 219 Latour J. M. 172 Latour S. 99 Lattke B. 331 L~u, P.-C. 286 Lau T. 238 Laubach B. 106 Laubli M. W. 11 Lauer M. 26 Lauer U. 192 Laufer P. 33 1 334 Lauffer R. B. 215 Launay J. P. 183 Laurent A. 296 Lavalette D. 222 Lavery A. 285 Law A. Y. C. 300 Law B. 336 Lawless J. 280 Lawrance G.A. 237 239 273 Lay K.-L. 190 205 Lay P. A. 237 238 256 261 273 Lazoryak B. I. 306 Leardini R. 33 Lebech B. 308 Lebioda L. 41 301 Le Blanc A. 328 Leblanc M. 162 Lec L. Y.C. 298 Lechat J. R. 279 Leclaire A. 280 Lecompte C. 220 Lecomte J. P. 259 Le Coq A. 134 Lednicky L. A. 216 Lednor P. W. 79 Lee F. L. 111 Lee H.U. 152 Lee L. 216 228 Lee M. 137 Lee M.E. 88 Lee R. 331,332 Lee T. J. 317 Lee V. Y. 137 Lee Y.J. 205 220 LeFGbre R. A. 218 Leger J. 328 Legler G. 333 Legrand A. P. 81 Lehman T. A. 102 Lehn J. M. 15 259 Leigh G. J. 3 184 Leitnaker J. M. 318 Lejay P. 20 3 15 Leligny H.,12 299 Le Marouille J.-Y. 243 246 Le Maux P. 202 Lemire A.E. 146 Lemke B. K. 236 Lemkuhl H. 65 Lemley J. T. 128 Lemmen T. H. 276 Lemmon R. M. 330 Lemos 0. F. 330 Lengel R. K. 277 Lenkinski R. E. 316 Lenstra A. T. H. 203 301 Lentz D. 140 158 161 Leonard J. E. 36 Leonelli J. 197 Leong A. J. 240 298 Leonhardt W. 109 Leoni P. 277 Leonowicz M. E. 129 Leopold D. G. 226 LePage Y.,78 111 Leporati E. 137 138 223 287 299 Leppkes R. 11 Lerch C. 109 Lerch P. 340 Leroy J. M. 319 Lerstrup K. 137 Lesch D. A. 141 243 260 Lesniak S. 296 Letafat B. 235 Letts J. B. 251 Leum E. 222 Leung W.-P. 181 Leupin P. 278 Levan K. R. 222 Levason W. 164 203 242 262 273 Levert J. M. 144 Levi H. 326 Levia M. 230 Levin V.I. 335 Levitt L. S. 149 Author Index Levy J. 81 Levy J. H. 161 318 Levy S. 333 Lewinski K. 301 Lewis D. F. 271 Lewis F. D. 22 Lewis G. E. 163 176 178 Lewis J. 205 247 248 252 253 254 292 Lexa D. 221 Lezama C. J. 337 Lhoste J. M. 222 Li B. L. 111 Li L. 222 Li Y.-J. 70 Liang B. F. 285 Libson K. 204 Lichen G. 225 Lichter R. D. 237 Lickiss P. D. 89 Liebau F. 67 Liebertz J. 296 Liebman J. F. 295 Liepins R. 27 Lin L. T. 88 Lin T. H. 337 Lincoln S. F. 282 298 323 Lindell E. 204 Lindeman S. V. 279 Linder L. 327 Lindgren T. 279 Lindmark A. F. 171 237 Lindoy L. F. 240,8298 Lindquist O. 289 133 Lindsell W. E. 202 260 Lindsey J. S. 298 Lindvedt R.L. 284 Linek A. 52 Linert W. 27 Ling R. G. 70 Linschitz H. 298 Linss M. 286 Lintvedt R. L. 284 Linz U. 337 Liotta F. J. 316 Lip H. C. 240 Lipka A. 114 Lippard S.J. 213 272 Lipscomb W. N. 12 Lipszyl H. 330 Lischewski M. 330 Lischka H. 88 Liss R. 332 Listovnichaya S. P. 19 Litman R. 342 Litthauer A. 166 Little F. E. 328 Liu C. 159 Liu C.-S. 207 Liu V. 112 Livermore J. 279 Livet J. 322 Livini E. 333 Livorness J. 285 Author Index 383 Li-Wu Yang 254 Ljones T. 288 Llobera A. 68 Llobet A. 297 Llorente A. 302 Lloret F. 212 214 Lloyd B. R. 266 Lobana T. S. 214 Lobanov A. A. 342 Lobartini J. C. 337 Lobkovskii E. B. 317 Lock C.J. 335 Lock C. J. L. 145 202 Lockhart T. P. 278 Loder J. 298 Lonnberg H. 283 Losch R. 150 Loew G. H. 280 Loiseau A. 66 Loiseleur H. 296 Lokhande R. S. 340 Loktyushina N. S. 310 Lomidze G. P. 19 Long G. J. 212 216 Long R. C. 285 Longoni G. 243,259 Loo B. H. 143 Lorenz B. 204 Lorenzini C. 236 Losalmonie A. 66 Losert W. 276 Lou J. 289 Louati A. 298 Louca P. 260 Loupec R. C. 150 Loy M. M. T. 150 Lozano R. 188 192 Lu P. 317 Luangdilok W. 220 Luboch E. 285 Lucas C. R. 201 Lucas J. 112 Lucas J. S. 23 Lucchesini M. B. 274 Lucci A. 20 Luchinat C. 287 288 Lucken E. A. C. 114 Lucy A. R. 228 289 Ludwig E. G. 114 Luescher E. F. 331 Luetgemeier H.3 12 Luetkens M. L. jun. 177 Lukas B. 285 Luke B. T. 5 Luksza M. 105 Luk'yanenko A. G. 329 Lumme P. 204 Luna D. 68 Lund W. 298 Lundeen M. 288 Lundstrom T. 19 Lunsford J. H. 234 Lusty J. R. 102 Lutsko V. 75 Lutz H. D. 73,98 130,296 Lutz V. H. D. 125 Lyding J. W. 94 Lykova L. N. 72 Lyle S. J. 310 31 1 Lynn J. W. 313 Lyons W. S. 326 Lysek M. 103 Lysyak T. V. 14 Ma E. C. 339 Maartensson N. 318 McAlister D. R. 127 227 Macarthy D. H. 242 McAteer C. H. 216 McAuley A. 242 McAulfie C. A. 203 268 McBride L. E. 329 McCallum J. D. 214 McCarron E. M. 111 191 McCarthy P. J. 171 McClelland B. W. 102 155 McCleverty J. A. 129 186 192 297 McClune C.J. 216 McClure D. S. 164 McConnell W. W. 230 MacCordick J. 310 McCudden B. 284 McCullough F. P. 262 McCullough K. J. 260 McCusker L. B. 251 McDaniel M. E. 288 McDermott D. P. 163 MacDiarmid A. G. 134 McDonald J. W. 193 223 McDonald R. N. 103 McDonald W. S. 45 50 265 MacDowell A. A. 197 McDowell M. S. 118 Mace J. M. 247 McElvany K. D. 334 McEwan D. M. 269 302 McFeely F. R. 296 McGlinchey M. J. 202 245 MacGregor R. R. 333 McHatton R. C. 238 Machida R. 235 Machilla H.-J. 333 Maciaszek S. 41 Maciel G. E. 96 McIntyre E. 331 McKee M. L. 77 McKee V. 12 285 McKenna P.J. 300 McKinnie R. E. 222 Mackinnon P. I. 323 McKissock A. 279 McLachlan S. J. 212 287 McLain S.J. 8 McLaughlan G. M. 237 McLaughlin J. G. 146 200 McLaughlin S. A. 248 MacLean G. K. 123 159 McLendon G. 21 1 McManus N. T. 263 McMaster A. D. 265 McMillin D. R. 277 McMullan R. K. 247 McMurry T. J. 205 McNulty G. S. 253 McPartlin M. 241 248 254 292 298 McPherson D. W. 77 McQuillen B. W. 167 McVey J. T. 343 McWhinnie W. R. 141 281 Maddock A. G. 340 341 Madic C. 322 Maeda M. 333 Maeda Y. 219 Maekawa H. 332 Maelia L. E. 223 Maercker A. 5 Maestri M. 237 Magarian R. A. 336 Maggiore C. J. 326 Maghrawy H. B. 342 Magini M. 225 281 Magnuson R. H. 256 Magnuson V. R. 41 Magon L. 322 Magurany C. J. 222 Mahadevan C. 296 Mahadevan M. 139 Mahajan D.235 260 Mahajan M. P. 281 Mahapatra P. K. 284 Mahdi R. T. 141 Mahen L. J. 132 256 Mahmoud M. M. 27 Mahy J. P. 219 Maier N. A. 56 Maier W. B. 239 Maier W. B. HI. 146 200 Maier-Borst W. 331 337 Mainka E. 325 Maisch R. 30 Maitlis P. M. 94 263 265 302 Majee B. 301 Majer V. 326 Majeste R. J. 278 Majumdar D. 25 Mak T. C. W. 290 300 302 Makarov V. S. 19 Makhaev V. D. 43 Makide Y. 327 Makino I. 326 Makoskaya 2. G. 76 Maksin T. 335 Malachowski M. R. 276 Maldotti A. 287 Maletina I. I. 146 Malik K. M. A. 185 288 Malik S. K. 315 Malikov D. A. 321 Malin J. M. 216 Author Index Malinin A. B. 328 Malinovski A. 187 Malinski T. 250 Malisch W.30 105 107 114 Mallouk T. 81 168 Malm J. G. 164 Malmquist P.-A. 166 318 Malone S. F. 302 Mal'tsev A. A. 310 Maltsev A. K. 88 Mamedov Kh. S. 67 Manabe O. 3 Manabue L. 281 Manassero M. 278 Mancilla T. 26 Mandal S. K. 285 Manes L. 319 Mangani S. 112 Manghi E. 320 Mangin D. 23 74 Mann B. E.,262 Mann K. R. 229 Mann S. 291 Manning A. R. 226 291 Manning M. C. 180 Manohar H.,280 Manoharan P. T. 242 Manojlovic-Muir L. 266 Manotti-Lanfredi A. M. 302 Mansuy D. 219 221 222 Mantle D. 222 Mantovani A. 281 Mantovani M. S. M. 343 Mao M. K. 334 Maqsudur-Rahman A. F. M. Maquestiau A. 106 Marafie H. M. 287 Marcellus C. G. 173 Marchand A. P. 336 Marchetti F.3 17 Marchon J.-C. 172 Marcomini A. 297 Marcotrigiano G. 281 283 Marcus Y. 325 Marder T. B. 199 Mardolini L. 14 Marek H. S. 171 Maretti M. I. L. 340 Margerum D. W. 102 148 242 286 Margerum L. w.,250 Margitan J. J. 149 Margrave J. L. 4 79 Mari A. 289 Mariam Y. 16 Marin J. M. 184 Marinas J. M. 68 Marinelli W. J. 149 Mannetti A. 245 Marini P. J. 127 223 Marino C. A. 333 335 Marinovich H. A. 211 Marko L. 233 Markovic M. 322 Markovski L. N. 106 Marks T. J. 43 94 324 Maroney M. J. 285 Marongiu G. 274 Maroto A. J. G. 211 Marquart R. 320 Marrese C. A. 112 Marsden C. J. 94 153 Marsden H. M. 80 Marsden K. 260 Marsh P. 299 Marsh R. E.,128 272 Marsh W.E. 278 286 Marsich N 277 Martell A. E.,215 237 285 Martella L. L. 329 Mdrtensson N. 166 Marti V. P. J. 36 Martin A. H. 238 Martin D. R. 21 Martin J. 237 Martin K. 274 Martin L. R. 245 Martin R. L. 237 307 Martinengo S. 258 259 289 Martinsen J. 241 Marton H. 74 Marty W. 238 Martynenko L. I. 146 Marumo F. 66 276 Maruyama Y. 336 Manilli L. G. 237 Mas C. 342 Masamune S.,82 83 84 99 Mascherpa G. 151 Masci B. 14 Masharak P. K. 224 Mashchenko I. V. 73 Mashima K. 172 Maslennikov V. P. 22 Mason J. 102 154 Mason M. G. 130 240 Mason P. A. 336 Mason R. 240 282 Mason W. R. 295 Massa W. 165 Massabri A. C. 279 Masse R. 289 Massey A. G. 41 152 Massey N.C.21 Massiari Y. 20 Masters A. F. 201 Matheson T. W. 249 Mathews N. F. 329 Mathey F. 109 251 Mathias C. 331 339 Mathiasch B. 101 Mathieu J. P. 330 336 Mathis C. 8 Mathis C. A. 339 Mathur P. 254 Matisons J. G. 246 MatkoviE-CalogoviC D. 301 Matsubayashi G. 287 Matsui K. 84 Matsumoto A. 3 15 Matsuura T. 338 Matsuyama M. 326 Matt G.N. 289 Mattern D. L. 149 Mattes R. 115 151 165 189 Matteson D. S. 25 Mattson B. M. 261 Matzanke B. 216 Mau A. W. H. 238 Maulik P. R. 297 Maurice A. M. 154 Mautner F. A, 4 Mauzerall D. C. 298 Maverick E. F. 3 Mawby R. J. 245 May A. S. 9 91 May P. M. 287 Maya B. M. 102 Maya L. 321 Maya W. 22 102 154 Mayibi M.113 Maynard R. B. 49 57 324 Mayr A. J. 243 Mazanec T. J. 251 Mazany A. M. 243 Mazicek J. 165 Mazibre M. 331 332 Mazurier A. 69 71 Mead K. A. 175 200 243 246 292 Medley J. H. 66 Mednikov E. G. 266 302 Medvedev V. A. 321 Meek D. W. 251 260 Meeker D. E. 101 Megahed Y. M. 337 M6gnarnisi-BClombt5 M. 278 279 Mehrotra S. K. 103 119 Meic Z. 301 Meidine M. F. 105 267 Meier P. 317 Meindl P. 8 Meiramov M. G. 58 Meissami N. 322 Melarango A. J. 336 Meli A. 41 129 236 240 277 Melikova Z. D. 71 Melius P. 77 Malmborg P. 332 Mel'mikova M. G. 72 Melnichenko E. I. 165 Melnik M. 280 Mel'nikova S. I. 23 Melton J. D. 235 Melzer D. 317 Memedovic T. V. 335 Menabue L.283,296 Meng R. L. 314 Merbach A. E. 317 Mercer J. R. 337 Author Index Mercer W. C. 260 Mercier F. 109 Mercier R. 11 5 Merideth C. W. 150 Mertens J. 336 Mertes K. B. 285 Mertz W. 182 Messbauer B. 266 Messer R. 321 Metcalfe K. 299 Metzger R. M. 163 175 Meullemeestre J. 278 279 Meunier B. 205 Mews R. 80 92 157 159 160 161 207 Meyer A. 107 Meyer B. 109 Meyer E. 332 Meyer E. F. I I2 Meyer G. 150 164 166 289 Meyer G. J. 331 332 Meyer H. 266 Meyer J. L. 4 Meyer P. 113 Meyer T. J. 217 250 Meyers E. A. 108 Meyers R. S. 221 Meyerstein D. 238 242 Micciche R. P. 48 49 Micera G. 140 287 Michael J. P. 130 240 Michalczyk M. J. 82 Michalopoulos D.L. 162 Michalowicz A, 280 Micheloni M. 240 282 Michl J. 82 83 Michman M. 41 Micskei K. 187 Midollini S. 41 11 1 129 243 263 264 277 302 Miessler G. L. 132 256 Mighell A. D. 286 Migita K. 236 Mignard M.,. 176 Mihichuk L. M. 323 Mikerin E. I. 330 Mikhailov Yu. N. 320 Mikhajlichenko A. I. 329 Mikheev N. B. 318 325 Miki K. 8 Mikulski C. M. 177 186 Mikuriya M. 282 Mile B. 276 292 Milenkovic S. M. 335 Milewski-Mahrla B. 107 115 Millar M. 223 Miller E. J. 234 Miller J. D. 141 217 Miller J. M. 21 316 Miller K. M. 222 Miller S. B. 53 Miller T. J. 25 28 Miller W. K. 192 Millikan M. B. 75 Millman S. E. 168 Mills C. F. 193 Mills R. M. 243 246 292 Mills S.L. 336 Millward G. R.,168 Milne J. 137 139 Milyukova M. S. 321 Mimoun H. 176 Mims M. P. 222 Minahan D. M. A. 268 Minami T. 3 Mingati C. 14 Minghetti G. 270 Mingos D. M. P. 132 267 289 292 Mink J. 301 Minkwitz R. 155 Mino Y. 215 Minten K. L. 268 Mirabal M. 31 1 Miran K. M. 337 Mironov K. E. 314 Mironov V. E. 74 Mironov Y. I. 144 Mironova A. A. 146 Misak N. Z. 342 Mispelter J. 222 Mistryukov V. E. 320 Mitani M. 278 Mitani Y. 68 Mitchell S. A. 278 Mitchener J. C. 226 Mitewa M. 187 Mit'kin V. N. 144 Mitra S. 339 340 Mitry E. 342 Mitschier A. 109 Mitsugashira T. 321 Mitta A. E. A, 335 Miura M. 22 Miura N. 312 Mix T. W.158 Miyai Y. 341 Miyoshi K. 238 287 Mizobe Y.,224 Mizuno K. 234 Mizuno M. 274 Mizutani N. 66 276 Mlekuz M. 245 Mo S. H. 339 Moattar F. 216 Mobley M. J. 150 Mochida K. 5 Mockler G. M. 214 Modak S. L. 297 Modonov V. B. 154 Moller W. 276 Moerlein S. M. 334 Motlat A. C. 336 Mogi H.,307 Mohai B. 187 Mohan N. 186 Moir J. E. 237 Moiseev D. P. 313 Mokhosoev M. V. 73 Mokokuma K. 233 Moller W. 135 Molloy K. C. 100 Molls M. 333 Molodkin A. K. 22 Molter M. 328 Momenteau M. 222 Monacelli F. 222 Monari M. 128 243 Moncorge R.,310 Mondal A. 135 Mondal J. U. 21 Mondal S. K. 123 Moneti S. 243 302 Monier J. C. 12 299 Monk C. B. 238 Monma M. 331 Monsef-Milzai P.281 Monsef-Milzai Z. 141 Montner S. M. 328 Moody D. C. 267 324 Moody R.,12 Moon S. D. 249 Moore E. P. 3 11 Moore H.A. 328 Moore I. 188 200 292 Moore K. J. 216 228 Moore P. 216 Moou D. 152 Moran J. R. 3 Morandini F. 251 Moras D. 15 Moratal J. 212 214 More K. M. 285 291 Moreau J. J. E. 89 Morelen S. 203 Moreless S. 130 Morf W. E. 11 Morgan T. V. 222 Mori W. 284 Morikawa A. 72 Morini P. 283 Morishima I. 281 Morozov B. A. 327 Morozova L. N. 302 Moms D. E. 217 Moms D. F. C. 343 Moms J. 247 Moms J. C. 149 Moms M. J. 246 Moms M. R. 242 Moms R. H. 184 267 Moms R. M. 219 220 Momson E. D. 263 Momson,'I. E. G. 225 285 Momson J.A. 41 Morse K. W. 41 275 Morss L. R. 319 321 Mortensen K. 137 Morton D. S. 217 Morton S. 268 Morvillo A. 114 Moser J. 318 Moshehalkov V. V. 315 Moss J. R. 200 252 Moss K. 291 Motekaitis R. J. 215 285 Mott G. N. 178 197 228 Motyl K. M. 229 Moulding R. P. 269 Moura H. I. 224 Mronga N. 204 Mrozek C. 274 Mrozihski J. 280 281 Muller A. 186 192 193 194 282 291 Muller B. G. 164 Muller D. 114 Muller E. W. 2 18 Mueller H. 340 Muller U. 162 204 Mueller W. 318 329 Mueller-Platz C. 333 Mueller-Platz C. M. 333 Muenze R. 335 Muth H. 284 Muetterties E. L. 85 245 Muhammad Bashees K. 278 Muir K. W. 97 266 Mukaida M. 249 Mukherjee D. 288 Mukerjee R. 250 Mulac W. A.261 321 Mullens J. 291 Muller A. 281 Muller G. 30 Muller H. 136 Muller K. 13 Muller U. 256 Muller W. N. 12 Mulvaney R. 297 Mura P. 263 Murai S. 232 Murakami S. 82 83 84 Muralikrishna C. 296 Murano Y. 333 Murata S. 287 Murchie M. 145 Murin A. N. 343 Murphy B. 277 Murphy J. L. 149 Murrall N. W. 242 Murray B. D. 9 104 105 227 Murray C. K. 242 Murray K. S. 127 223 Murray R. W. 250 Murray S. G. 268 Murrell J. N. 3 Muruyama Y.,332 Musikas C. 322 Musinu A. 281 Musumeci S. 283 Mutikainen I. 204 Muto M. 62 Muto T. 340 Mtetwa. V. S. B. 174 Myakshin I. N. 144 Myasoedov A. B. 146 Myasoedov B. F. 321 342 Myers R. D. 114 144 Naagren K. 332 Naesman P. 335 Nag K. 123 285 Nagai Y.82 Nagaoka Y. 336 Nagarajan R. 314 Nagase S. 88 Nagel C. C. 248 Nagl A. 301 Nagypal I. 187 280 282 Naish P. J. 242 246 Naithani A. K. 34 Najjar R. C. 177 179 Nakadaira Y. 86 Nakajima T. 169 Nakamoto K. 205 Nakamura A. 235 Nakamura M. 62 282 Nakaoka H. 332 Nakata M. 235 Nakatsuji Y. Nakayama T. 332 Nakazawa H. 271 Nakazawa M. 326 Naldini L. 278 Nancollas G. H. 4 Nandana W. A. S. 114 151 Nandi S. 294 Nanjundaswamy K. S. 67 Nanninga D. 30 3 1 32 Naqvi S. 1. I. 341 Narayana P. A. 281 Narayanaswamy R. 227 Nardi N. 236 Nardin G. 283 Narten A. H. 321 Nascimento 0. R. 279 Nasser F. A. K. 100 Naumann D. 157 Naumann R. 23 Navarro N. J. 328 Navaza A. 320 Nave S. E. 318 Navratil J.D. 329 Nazran A. S. 78 Neamtu M. 177 Neaves B. D. 188 Neckel A. 27 Neer G. L. 216 Nefedov 0. M. 88 Nefedov V. D. 325 Neffe G. 342 Neidle S. 273 Neilson R. H.,111 Neirinckx R. D. 328 Nejedly Z. 332 Nel A. 183 Nelson C. D. 269 Nelson G. O. 230 Author Index Nelson J. H. 251 Nelson P. G. 68 163 Nelson S. M. 12 218 277 285 Nelson W.J. H. 247 248 253 254 292 Nemeh S. 262 Nemo T. E. 221 Nepveu F. 284 Nesmeyanov A. N. 338 342 Nesterova N. P. 342 Neuenschwander K. 226 Neugebauer D. 30 107 138 141 212 Neugebauer W.,4 5 Neumann W. P. 88 Neve F. 264 283 Newberry V. F. 203 Newcomb M. 99 Newell P.A. 338 Newkome G. R. 279 Newnham R. E. 69 Newton G. W. A. 330 Newton W. E.193 223 Ng B. W. 241 Ng C. Y. 215 285 Ng J. S. 333 Ng K. S. 8 Ng W. W. 8 Nguyen M. T. 78 Nguyen V. N. 315 Nguyen Huy Dung 320 Nhan D-D. 144 337 Nicholls D. 297 Nicholls J. N. 248 292 Nichols B. S. 263 Nicholson B. K. 243 292 Nicholson J. R. 129 193 276 277 Niecke E. 29 109 113 Niedenzu K. 29 Niedrich H. 330 Nieke E. 103 Nielson A. J. 185 191 Nielson L. 310 Nieter Burgmayer S. J. 189 Niethammer T. 332 Nieuwpoort G. 281 Niisawa K. 331 Nikolaev A. N. 155 Nikolaev E. N. 306 Nikolenko L. N. 146 Nikolics K. 330 Nikolotova Z. I. 329 Nikolov G. St. 281 Nilsson J. L. G. 331 Nilsson K. 275 Nilsson M. 275 276 Nishihara Y. 329 Nishioji H. 340 Nishiwaki K. 240 Nishizawa S. 313 Nisseren D.A. 101 Nitsche H. 342 Author Index Niven M. L. 252 Nixon J. F. 105 267 Noakes D. R. 313 Nojima M. 22 Nokami J. 61 Nolan K. B. 219 299 Noll B. 335 Noltemeyer M. 92 112 119 134 160 179 291 Nomoto K. 215 Nomura O. 233 Noordik J. H. 292 294 Nord G. 217 264 Nordeen S. K. 337 Nordine P. C. 309 Norem N. 227 296 Noreus D. 309 Norman N. C. 97 103 104 107 198 227 260 Norseyev,Yu. V. 144,337,341 Narthcott D. J. 78 Nortia T. 279 Norton R. J. 97 201 Nosca D. L. 237 238 Noskovii D. 301 Noth H. 29 33 Nothe D. 282 Now E. M. 145 Novak C. 52 Novotortsev V. M. 279 Nowell I. W. 300 Nowmand M. 322 Nowogrocki G. 74 186 Nowotny H. 4 Noyce J. R. 329 Nozaki T. 331 333 Nozawa T.235 Numisto L. 320 Numata M. 279 Nunn C. M. 200 292 Nuss D. M. 21 Nutkovich M. 238 Nutsubidze P. V. 319 Nutton A. 263 Nuzzo R. G. 241 Nyburg S. C. 8 84 Oakes J. 214 Oakley R. K. 122 173 Obendorf D. 301 Oberdorfer F. 331 332 Oberhammer H. 152 O’Brien H. A. jun. 327 328 O’Brien P. 229 284 Ochrymowyn L. A. 282 O’Cleirigh D. A. 297 O’Con C. A. 54 O’Connor C. J. 214,278 O’Connor M. J. 199 201 280 Odashima T. 307 Odenheimer B. 337 Odika T. I. 230 O’Donnell T. A. 162 166 265 318 O’Donoghue M. W. 176 O’Donoghue T. D. 205 Oener A. M. 309 Oesterreicher H. 309 Offergeld G. 274 Offerman W. 291 Oft B. 73 130 Ogata N. 341 Ogawa N. 5 Ogden J. S. 164 167 203 310 Ogle C. A. 130 236 282 Ohman L.O. 62 Ohmomo Y. 333 Ohshio H. 219 Ohtani T. 20 Ohtsuka Y. 68 Oizumi K. 68 Okamoto M. 329 Okamoto Y. 8 187 Okawa H. 280 282 Okawa T. 82 Okawara R. 61 Okazaki H. 237 Okazaki S. 327 Okeya S. 263 Oksam A. 226 Okura N. 277 Ol’dekop Yu. A. 56 O’Leary A. 282 Oleinik I. I. 74 Oleksyszyn J. 114 Oliver J. P. 266 302 Olivier M. J. 99 Olivier-Fourcade J. 74 Olmstead M. M. 9 10 104 105 227 261 269 Olsen J. S. 222 Olsher U. 12 Olsson L. G. 309 Olszanski D. J. 216 Onak T. 47 50 O’Neal H. R. 111 O’Neill M. E. 38 Ono F. 326 Oonishi I. 28 Ora L. A. 292 Orcutt J. A. 343 Orda V. V. 146 O’Reilly E. J. 17 Orioli G. A. 337 Orlandini A. 41 111 129 263 264 277 Orlova G. M.75 O’Rourke C. 227 296 Orpen A. G. 242 246 247 253 266 292 Orrell K. G. 201 234 274 Orsini J. 286 Ortiz de Montellano P. R. 219 Osborne J. H. 132 138 264 O’Shea M. T. 214 281 Oshikawa T. 65 Osin S. B. 310 Oskam A. 228 Osso J. A. 330 Osterholz A. 332 Osterwalder J. 309 Ostvold T. 62 Ota N. 215 Otera J. 61 Otero Diaz C. 3 13 Otozai K. 337 Otsuka R. 72 Otsuka S. 262 277 Ott H. R. 309 Ott M. A. 328 Otterbein E. S. 252 Ouderkirk A. J. 226 Ousaka Y. 3 12 Ouvard G. 124 Ovchinnikov K. V. 306 Overberger C. G. 38 Overfeld R. E. 17 Owen J. D. 12 14 Oxman J. D. 22 Oye H. A. 69 Ozarowski A. 285 Ozawa F. 63 271 Ozawa T. 298 Ozin G. A. 278 Ozolins G. 23 Paans A. M. J. 327 332 Pace L.J. 241 Pace S. 30 112 Pacer R. A. 329 Paden S. 238 Paderno Yu. B. 19 Padgett H. C. 331 Paetzold P. 28 29 Paez D. E. 249 Paffett M. T. 182 Page D. R. 237 Page E. M. 117 164 Page T. H. 117 295 Pages M. 117 140 166 319 Pagni P. G. 334 Pahl C. 106 260 Pahor N. B. 283 Paine J. B. III. 298 Pakawatchai C. 72 275 Pakulski M. 103 104 105 227 Palazzi A. 128 243 Palazzotto M. C. 229 Palchan I. 81 168 Palermo R. E. 194 Palladio D. P. 33 Palmer A. J. 332 Palmer S. M. 241 Palosz B. 299 Palyi G. 233 Pampaloni G. 180 Pande S.,329 Pang H. 204 Pannell K. H.,227 243 Pannetier J. 295 387 Panyushkin V. T. 307 Panzanelli A. 278 287 Paoletti P. 240 Paonessa R. S. 270 Papaefthymiou G.C. 126 Papaefthymiou V. 127 224 Papasergio R. I. 6 89 277 Pappalardo G. C. 108 Pardo M. P. 73 300 314 Parge H. E. 51 294 Parge H. W. 97 Parise J. B. 296 Parish D. W. 219 Park J. M. 78 Park M. N. 354 Parker D. 259 Parkey R. W. 336 Parkin S. S. P. 137 Parkinson J. E. 149 Pams K. D. 144 Parry R. W. 240 Parthe E. 66 315 Pascal J-L. 149 Pascard C. 259 Paschina G. 225 281 Pasquali M. 276 277 Passaretti J. 132 Passmore J. 114 123 136. 145 151 158 159 Pasynskii A. A. 279 Patch M. G. 215 Patel K. C. 278 Patil S. F. 339 Paton J. D. 279 Patra M. 284 Patrick J. M. 246 31 1 323 Pau C. F. 88 Paukov I. E. 308 Paukovic N. 322 Paulen W. 80 106 109 Paulissen M. L. H. 292 Paulus H.284 Paulus J. M. 341 Pawl J. C. 324 Pawelke G. 155 Pawley G. S. 161 Payne J. D. 232 289 Payne M.P. 324 Payne N. C. 277 Payne S. A. 164 Peacock R. D. 237 Peake B. M. 226 Pearce C. J. 35 Pearse R. V. 68 163 Pearson K. H. 3 15 Pearson R. G. 243 Pearson T. R.,277 Pebler J. 30 34 219 Pecoraro V. L. 2 15 2 I6 Pedersen A. S. 308 Pedersen B. 217 Pedersen E. 191 Pedersen J. D. 251 Pedersen L. G. 102 Pelikan P. 278 Pelizzi C. 100 236 Pelizzi G. 100 114 180 236 237 Pelizzone M. 306 Pellacani G. C. 281 283 296 Pellinghelli M. A. 137 138 223 287 299 Peloso A. 295 Pena J. P. 58 Penfold B. R.,165 182 265 Peng G. T. 330 Pennell C. A. 237 Penneman R. A. 319 320 Pennesi G. 118 222 Pennington W.T. 122 173 Perega G. 3 17 Perepelitsa A. P. 76 Perez G. V. 334 Pergola R. D. 243 258 259 Peringer P. 301 Perkins C. M. 130 282 Perkins P. G. 19 27 Perkins T. 221 Pernin C. 330 Perotti A. 285 Perry D. L. 137 223 Pertici P. 249 Perun L. A. 332 Peruzzini M. 111 124 260 Pestunovich V. A. 154 Pet R. 294 Petch E. A. 27 Peterman D. J. 308 Peters H. 268 Peters J. A. 9 Peters J. M. 332 Petersen J. D. 216 228 Peterson D. T. 308 Peterson J. R. 166 318 319 322 Peterson R. E. 333 Peterson W. 13 Petricek V. 39 Petrignani J-F. 198 Petro W. J. 88 Petrouleas V. 127 224 Petrov K. I. 23 73 Petrov V. M. 162 Petrova L. A. 67 Petrova D. V. 22 Petrova V. N. 162 Petrovskii P. V. 302 Petry R.F.,328 Pett V. B. 282 Petter W. 140 Pettit L. D. 288 Pettman R. B. 219 Petzel T. 305 Petzold G. 337 Petzold G-S. 334 Peymann E. 291 Peyrard J. 312 Author Index Peyronel G. 275 297 Pezeshk A. 288 Pezzei G. 11 301 Pfahl K. M. 180 Pfeffer M. 7 Pfeiffer M. 144 337 Pfkter P. M. 132 Phelan D. 22 283 Phelan K. G. 102 Philippot E. 74 Philips C. A. 284 Phillips L. 229 Phillips T. D. 354 Philocke-Levisalles M.,280 Piccaluga G. 225 281 Pichon R. 174 Pickel P. 94 Pickett C. J. 188 Pierce J. L. 291 Pierce-Butler M.A. 268 Pierre J. L. 292 Pigford T. 326 Pignolet L. H. 132 256 261 292 Pihlaja K. 279 Pike M. M. 316 Pike V. W. 331 332 Pilbrow J. R. 285 Pilipovich D. 22 102 154 Pilkington N.J. 263 Pimental G. 337 Pin W. H. 129 Pinkert W. 125 291 Pinna G. 225 Piovesana O. 213 280 Pirakitigoon S. 155 Pirozhkov S. V. 335 Pisaniello D. L. 282 317 Pisareva 1. V. 59 Pistark s. 167 Pityulin A. N. 20 Pizzey M. 323 Pizer R. 24 316 Plaas D. 246 Planalp R. P. 91 Platt A. W. G. 156 274 Pleiss U.,330 Plesek J. 49 Plews M. J. 323 324 Plotkin J. S. 94 48 230 Pluciennik H. 330 Plummet D. T. 226 Pocker Y. 298 Podlahovi J. 301 Poe A. 207 Poggi A. 285 Pogorelov A. G. 61 Pohl S. 6 103 114 Poilblanc R. 249 Pojer P. M. 335 Pokrovskii A. N. 306 Pola J. 20 Polak P. 327 Polesak H. 27 Author Index Polevoj A. S. 326 Polgar J. 282 Poli R. 114 Poliakoff M.146 200 207 239 Polishchuk S. A. 165 Polla G. 320 Polyakova V. B. 61 Polyanskaya 0. V. 311 Polyukhov V. G. 343 Pomeroy R. K. 95 245 253 Pommerening H.,114 Pommier J-C. 336 Poncet J-L. 178 Pontzen T. 92 109 Poon C.-K. 238 264 Poon Y.L. 84 Poonia N. S. 11 Pople J. A, 5 Popov A. I. 14 167 Popova I. Yu. 62 Popovic S. 71 Popovitch V. B. 328 Porotnikov N. V. 72 73 Porter L. C. 280 Porter W. A. 237 Porter W. R. 333 Porzio W. 249 Postgate J. R. 352 Postma R. 12 297 Potenza J. A. 283 Potier J. 149 150 Potter P. E. 325 Potts A. W. I14 Potzel W. 3 18 Poveda M. L. 184 Povey D. C. 197 Powell D. R. 147 Powell G. L. 199 206 Powell J. 8 271 Powell W. H. 36 Power P. P. 5 9 97 104 105 227 Powers L.298 Prach T. 336 Pramanik P. 6 135 Prampolini P. 283 Prasad L. 40 323 Prasada Rao M. S. 74 Predieri G. 236 Preetz W. 163 256 Pregosin P. S. 270 302 Prenant C. 331 332 Preston P. N. 241 Preut H. 100 Prewitt C. T. 296 299 Priester R. D. 66 Pringle P. G. 266 269 302 Priolo F. C. 284 Pritt J. W. 222 Pritzkow H. 33 34 97 Privalova P. A. 343 Prokof’ev A. I. 154 Prosperi T. 282 Protiva J. 330 Proud,‘G. P. 129 193 224 Prout K. 174 Prud’homme 93 Prusakov V. N. 162 Puddephatt R. J. 257 266 269 295 Puetter D. 328 Puga J. 247 248 253 292 Pujari M. P. 235 Purcell W. L. 238 Puri J. 316 Purrello R. 283 Putilin S. N. 306 Putnis A. 96 Pyatenko A. T. 166 Pynn R. 3 13 aim S.M. 328 $xun S. 328 Quaglia L. 332 Quarton P. M. 279 Que L. 215 Quezel S. 314 Quilichini M. 295 Quinton M. F. 81 Raap A. 190 Raban M. 14 Rabenau A. 152 321 Rabinovitz M. 81 Rack E. P. 339 Rackley B. G. 58 Radhakrishna P. 308 Radlowski C. A. 238 Rae A. D. 282 291 301 Rae A. E. 186 Raghavachari K. 36 Ragimova D. M. 71 Rai D. 321 Raine G. P. 79 Raithby P. R. 205 247 248 252 253 254 276 292 Rakov E. G. 165 Rakowski DuBois M. 182 Rakitin Yu. V. 279 Ram M. S. 238 Ramachandran K. 1 12 Ramakrishna B. L.,242 Ramana K. V. 74 Ramaniah V. 307 Ramasami T. 239 Ramette R. W. 278 Ramirez M. L. 188 Randall M. L. 238 Ranft Z. 150 Rankin D. A. 265 Rankin D. W. H. 93 94 108 124 156 157 263 Rao B.S. M. 339 Rao M. N. S. 113 Rao U. R. K. 165 Rao V. M. 280 Raos N. 288 Rappo A. V. 31 1 Rasey J. S. 334 Rassu G. 296 Raston C. L. 6 9 89 91 181 275 277 Rasula N. 31 1 Rauchfuss T. B. 141 179 243 260 264 Rauchschwalbe U. 3 14 Rausch M. D. 173 Rava R. P. 252 Ravet-Krill M. F. 312 Ravez J. 299 Ravot D. 314 Ray R. 25 Raymond K. 334 Raymond K. N. 215 216 237 Razay H. 243 Razi T. 294 Read R. A. 242 Rebizant J. 319 324 Recktenwald O. 97 Reddy A. S. 328 Reddy B. R. 328 Reddy M. L. 328 Redlich W. 305 Reed F. J. S.,263 Reedijk J. 218 277 278 281 283 284 301 Rees L. V. C. 338 Reeves R. L. 242 Reger D. L. 41 172 231 Rehder D. 180 Rehorek A. 276 Rehorek D. 276 Rehwoldt M.317 Reid C. 335 Reid M. F. 307 Reid R. S. 303 Reiff W. M. 130 212 234 Reihl B. 319 Reimer K. J. 222 Reiner D. 141 Reinhammar B. 288 Reinhoudt D. N. 14 Reivich M. 331 Renault H. 333 Renkema W. E. 238 239 Rentzepis P. J. 277 Reshetnikova L. P. 66 Ressner J. M. 184 Rest A. J. 227 Retta N. 107 Rettig,S. J.,30,31,32,91,172,260 Reuschenbach G. 109 Reutov 0. A. 302 Rey N. 74 Reynhardt E. C. 163 Reynolds G. 62 Reynolds P. A. 240 Reynolds S. J. 186 Reynolds W. L. 238 Rheingold A. L. 114 175 179 229 230 234. 260 Author Index Rhodes R. K.,220 Ribeiro F. B. 343 Rice D. A. 117 164 165 Rice S. F. 272 Richard P. 178 Richards J. H. 221 Richards P. 329 336 Richards R.L. 128 193 Richardson J. F. 113 120 121 Richardson M. F. 171 Richardson R. S. 307 Riche C. 221 Riche F. 336 Richman J. E. 11 2 Richter A. 146 Richter H. 113 Rieck D. 163 Riess J. G. 30 112 Rietmeijer F. J. 278 Rietz R. 166 318 Riffel H. 288 Riley P. E. 237 Rillema D. P. 250 Ring J. 342 Ringel H. 342 Ritchey J. M. 267 Ritchie L. D. 229 Ritchie V. S. 287 Ritter G. 218 Riviere P. 89 Rizkalla E. N. 316 Rizzardi G. 284 Rizzarelli L. 283 Robb D. A. 22 Robenstein D. L. 303 Robert T. 274 Roberts A. J. 197 Roberts B. P. 35 36 Roberts D. A. 235 263 Roberts H.L. 278 Roberts J. A. 337 Roberts M. M. 272 Robertson B. E. 323 Robertson D. W. 330 Robertson H. E. 93 108 124 I56 Robinson B.H.,233 Robinson D. J. 265 Robinson G. D. 331 Robinson J. M.,317 Robinson R. 297 Robinson S. D. 257 Robinson W. R. 256 286 Rocks R. D. 25 Rodesiler R. F. 299 Rodger C. 202 Rodgers J. 237 Rodier N. 313 314 Rodley G. A. 17 Rodon A. 327 Rodriguez A. G. 334 Rodriguez de Barbarin C. O. 12 Roe D. C. 183 Roecker L. 237 Roeda D. 332 Rosch F. 144 337 Rosch L. 101 Roschenthaler G. V. 108 156 Roesky. H. W.,92,112 119 123. 125 134 179 291 296 297 Roessler K.,331 339 Roge G. 100 Rogers D. 202 Rogers P. S. Z. 326 Rogers R. D. 66,91 173 184 Rohde B. M. 16 Rohde C. 4 78 Rohwer H. E. 166 Rojo T. 283 297 Rokos A. 336 Roman J. 192 Romanenko V. D. 106 Romanov G. V. 144 Romeo M. 283 Romiti P.204 Ronai A. 330 Ronge K. 307 Roos B. 101 Root J. W. 339 Roper W. R. 80 Roques R. 275 Rorabacher D. B. 282 Rosales M. J. 248 253 292 Rose M. E.,15 Rose N. J. 217 218 Rose P. S. 14 Rosen A. M. 329 Rosenberg E. 246 302 Rosenhein L. D. 231 Rosenthal S. 333 Rosetti R. 243 Rossat Mignod J. 314 315 Rosseinsky D. R. 228 Rossell D. 302 Rossi G. 118 222 Rosso U. 216 Roth W. J. 163 176 179 Rothman L. S.,327 Rothwell 1. P. 196 Rotondo E. 284 Rottenberg D. A. 332 Rotzinger F. P. 235 286 Roulet R. 279 Roult G. 74 Roundhill D. M..133 264 272 282 Rousseau .I. 205 334 Roustan J. L. A. 227 Rouxell J. 124 Rowan N. S. 237 Rowland F. S. 339 Roy A. 201 Roy R. 63 123 Roziere J.137 Roznyatovskii V. A. 59 Ruban A. V. 106 Rudman P.S. 309 Rudolf P. 237 Rudolph R. W. 38 57 Rudzinski W. E. 284 Ruger R. 103 109 113 Ruf H. 325 Rufinska A. 65 Ruger R. 29 Ruhl D. 151 Ruisinger B. 81 Ruitenberg K. 278 Rumpel H. 114 Rupp-Bensadon J. 114 Rusakov S. L. 74 RuSEiC B. 167 310 Rush J. D. 292 Rushman P. 95 245 Russell C. D. 334 335 Russell D. R. 164 Russell G. A. 301 Russev P. 187 Russo M. V. 241 Rustamov P. G. 71 Rustichelli F. 319 Ruth J. L. 332 Ruzic-Toros Z. 71 Ryabinin A. I. 341 Ryabov A.-D. 48 Ryan J. L. 321 Ryan M. 127 225 Ryan R. R. 267 324 Rycroft D. G. 112 Ryschkewitsch G. E. 28 Ryzhov M. G. 285 Rza-Zade P. F. 67 Sabaev I. Ya. 62 Sabat M. 225 Sabatini A.240 282 Sadanani N. D. 108 Sadek S. A. 334 Sadhu K. M. 25 Sadhukhan H. K. 327 Sadler I. H.,258 Sadler P. J. 273 294 295 Saebo S. 27 Saenger W. 13 Safonov A. V. 327 Saftic B. 3 11 Sagarik K. P. 16 Sagi S. R. 74 Saha N. 288 Sahbari J. J. 9 10 Sahm M. 284 Sahu R. D. 297 Saillard J-Y. 245 Saito E. 8 Saito J. 331 Saito K. 239 Saji H. 333 Sakaba H. 86 Sakaeda T. 262 Sakaguchi T. 296 Sakaguchi U. 237 Sakai K. 327 Author Index Sakai M. 341 Sakai O. 3 12 Sakai Y.,340 Sakamoto H. 15 326 Sakarnoto K. 85 Sakane K. 341 Sakuma Y.,329 Sakurai H. 85 86 Sakurai T. 281 Saladini M. 283 Salah B. 300 Salaiun J.-Y. 175 243 Salajan M. 115 Salazar K. V. 324 Salem G.302 Salen R. M. 61 Salentine C. G. 23 Salter I. D. 246 247 Salvadori P. A. 333 Salvatore F. 322 Sambale C. 228 Sammartano S. 283 Sampathkumaran E. V. 3 14 Sams J. R. 222 279 Samuel D. 11 Samuel E. 174 Samways B. J. 97 Sanchez J. P. 310 Sandelesen R. 177 Sanders W. M. 70 Sanders-Loehr J. 214 Sanderson L. J. 261 Sandhu S. S. 214 Sandrini D. 237 Sandrock G. D. 309 Sandstrom M. 75 Sanemasa I. 288 San Filippa J. jun. 252 Sangster D. F. 238 Sano M. 124 Santandrea R. 276 Santarsiero B. D. 127 227 Santos A. 302 Santos R. H. A, 279 Saporovskaya M. B. 285 Sapozhnikov Yu. A. 342 Sappa E. 243 Sapse A. M. 134 Saracuglu A. I. 299 Sargeson A. M. 237 238 239 26 1 262 273 Sarkar A. R.288 Sarkar K. K. 301 Sarkar S. 186 192 Sartorelli U. 258 Sarvin A. P. 162 Sasaki K. 341 Saseki Y. 239 Sasse W. H. F. 238 Sastre J. 331 332 Sastry K. A. R. 26 334 Sastry M. D. 165 Sastry S. 296 Sastry U. 26 Sasvari J. 70 Sata M. 126 Saterlee J. D. 222 Saterlee J. T. 221 Satge J. 89 Sathyanarayana D. N. 280 Sato A. 321 Sato S. 9 Sato T. 63 Sattelberger A. P. 177 Sattler E. L. 331 Sau A. C. 110 Saulys D. A. 41 Saunders D. R. 245 Saur Ch. 312 Saussine L. 176 Saveant J.-M., 221 Savenot N. B. 341 Saw C. K. 305 Sawada K. 296 Sawaoka A. 308 Sawyer D. T. 287 297 Sawyer J. F. 301 Sawyer L. 249 Saxton R. J. 137 Saxton R. L. 223 Sayer B. G. 202 245 335 Saylors M. L. 168 Sbrana G.261 Sbrignadello G. 323 Scaramuzza L. 133 274 Schaaf T. F. 302 Schachschneider G. 337 Schack C. J. 80 140 148 155 Schafer? A. 82 Schaefer H. 14 136 138 150 Schafer W. 109 Schaefer W. P. 272 Schaffer A. 95 Schaffer C. E. 237 Schaeffer H. F. 79 88 107 Schallenberg J. 332 Schammel W. P. 216 Schat G. 98 172 Schatz P.-N., 226 Schawrzmann E. 62 Schefer J. 308 309 Schemer T. B. 163 Scheidt W. R. 44,205 Schell-Sorokin A. J. 150 Schenk H. J. 341 Schenk W. A. 201 Scherer 0. J. 92 113 Schen A. 17 Schick G. A. 222 Schiedt W. R. 220 Schieferdecker H.,325 Schier A. 5 107 Schiffini L. 20 Schildercrout S. M. 222 Schimanski U. 193 194 281 282 291 Schimitz J. E. J. 292 39 1 Schimkowiak J.291 Schimpf R. 183 Schindler R.-N., 149 Schings U. 92 Schirber J. E. 305 Schlapfer C. W. 278 302 Schlapbach L. 309 Schleyer P. von R. 3 4 5 20 34 36 78 Schlogl R. 81 168 Schluter E. 6 Schlyer D. J. 332 333 Schmall B. 331 332 Schmehl R. H. 250 Schmid E. 30 Schmid G. 29 Schmidbaur H.. 5 8 30 68. 107 115 125 138 212 295 Schmidpeter A. 113 Schmidt A. 114 115 Schmidt E. 14 Schmidt F. A, 305 Schmidt H. G. 92 119 139 179 291 Schmidt K. 204 Schmidt K. H. 321 Schmidt M. A. 232 Schmidt M. S. 231 Schmidt T. 109 Schmidt-May J. 3 13 Schmitz D. 28 Schmulbach C. D. 163 176 Schmutzler R. 108 156 Schneader M. L. 10 Schnering H.G. V. 135 Schoch K. F. 94 Schock L. E. 8 Schoeller W.W. 103 109 Schollhorn R. 162 Schoen J. 325 Schoenes J. 320 Schoening R. C. 258 Scholand H. 189 Scholl H. 334 Schomaker V. 127 227 Schomburg D. 93 108 153 156 Schrenk J. L. 229 Schriewer M. 88 Schrobilgen G. J.. 147 333 335 Schrock R. R. 187 Schroder M. 248 Schroder F. A, 299 Schuberd U. 5 Schubert B. 6 Schubert P. F. 207 Schubert U. 4 7 34 267 Schueller M.,333 Schuger H. J. 283 Schultz G. 88 Schulz R. A. 13 Schulz A. J. 274 Schultz N. L. 226 Schurnacher G. A. 147 Schurnaker R. R. 137 Schwalke M. A. 112 Schwanker R.,31 1 326 Schwartz K. B. 296,299 Schwarz H. 41 Schwarz H. A. 261 Schwarz W. 114 115 Schwanmann E. 114 289 Schweizer H.-J. 150 Schwing M. J. 278 279 Schwing-Weill M.J.316 Schwochau,*K. 334,341 Schwotzer W.,163 176 199 Scopelianos A. G. 58 Scott P. L. 21 Scozzafava A. 287 Scrita R.,14 Scudder. M. L. 129,282 287 291 299 Seaborg. G. T. 325 Seadon J. K. 277 Seaverson L. M. 171 Secco A. 100 Sew M. 302 Secomb R.,299 Seddon K. R. 163 269 Sederel L. C. 333 Sedlak D. 33 Sedov A. 283 Seebach D. 6 Seeberger M.H. 90 260 Seetz J. W. F. L. 98 172 Seevers R. H. 334 Seff K. 251 283 Segmuller B. E. 254 Seibl J. 284 Seidel A. 325 Seifert F. 67 Seifert S. 335 Seiwert F. J. 300 Sekhar C. 207 Seki H. 341 Sekiguchi A. 86 Sekine T. 340 Selbin J. 187 Seleznev A. G. 318 Selig H.,81 168 Sellmann D. 188 Selwyn A. P. 331 Selzer R. 316 Semenenko K.N. 43 67 Semenov G. A. 306 Semmelhack M. F. 227 Sena S. F. 229 Sendelbeck R. 301 Senderoff S. G. 334 Sengupta A. 163 Sengupta K. K. 294 Sengupta S. 294 Seno M.,15 Senoff C. V. 268 Sensui Y. 338 Sentic B. 71 Sepelak D. J. 5 Seppelt K. 79 140 158 161 Serrano J. 340 Serrano R.,95 Seshasayee M.,296 Sessler J. L. 219 220 Setchell C. 62 Setton R. 81 Setzer W. N. 130 236 282 Severengiz T. 109 114 Severson S. J. 240 Sevryukov N. N. 61 63 Seward E. 37 Seyer U. 186 Seyferth D. 5 93 99 243 302 Shafik A. 342 Shah V. K. 249 Shakir R.,9 91 Shalaby A. M. 337 Shamala N. 17 Shamin A. 298 Shamshoum E. S. 199 Shannon R. D. 296 299 Shantha Nandana W. A. 136 Shanzer A. 11 Shaplygin I.S. 69 Shaposhnitov A. V. 62 Sharifov Ya. N. 71 Sharkov S. A. 146 Sharma K. K. 74 Sharma P. D. 280 Sharon M. 341 Sharp A. 17 Sharp D. W. A. 163 Sharp P. R. 197 229 286 Sharpe N. W. 100 Shaughnessy W. J. 332 Shaw B. L. 266 269 302 Shawali A. S. 287 Shcherbakov V. A. 20 Shcherbina T. M. 48 Shea J. A. 148 Shearer H. M.M.,4 10 43 297 Sheh Y. 327 Sheikh B. 262 Sheldon R. I. 285 Sheldrick G. M.,62 80 92 112 114 115 119 125 134 159 160 179 207 246 289 291 293 295 299 Sheldrick W. F. 355 Sheldrick W. S. 13 Shelnutt J. A. 222 Shelton R. N. 306 Shenoy G. K. 313 314 Shepherd R. E. 238 Sheridan J. B. 228 Sheridan J. J. 111 309 Shevchenko Yu. N. 59 Shevlin P. B. 77 Author Index Shibaeva R.P. 276 301 Shibagaki A. 296 Shibata S, 28 Shibayama K. 103 109 125 Shida T. 261 Shields G. D. 287 Shikh I. V. 319 Shimada M. 20 Shimizu H. 287 Shimizu T. 17 299 Shimoi M. 37 38 Shimomoto R.,43 Shimozawa R.,242 Shinkai S. 3 Shinohara M.,333 Shinomoto R.,172 Shiokawa J. 3 15 Shiokawa Y. 321 Shiou-Jyh Hwu 31 1 Shiralian M.,245 Shirazi A. 222 Shirk A. E. 20 Shirk J. S, 20 Shirokii V. L. 56 Shine C.-Y. 146 333 Shklover V. E. 279 Shklovskaya R. M. 75 Shohan G. 12 Shone M. 226 Shong R. G. 227 296 Shono T. 15 Shore S. G. 44,230 248 Short R. L. 178 185 191 Shreeve J. M. 80 103 148 154 158 Shubina T. S. 305 Shugong Zhang 3 17 Shuiyu Cai 309 Shulman P. M. 263 Shumilin E.N. 342 Shunsaku S. 341 Shushakov V. D. 318 Shushakova T. V. 318 Shustov L. D. 146 Sibley C. A. 222 Sidahmed I. M. 238 Sidorenko G. V. 322 Sidorov L. N. 167 Siebert W. 33 34 97 Siedle A. R. 283 286 Siefert E. E. 338 Sienko M. J. 313 314 Severs R.,106 Siftar J. 72 Sik V. 201 Sikirica M. 301 306 Sikora D. J. 173 Silina E. 23 Sillanpaa R. 279 Silva R.,342 Silva-Trivino L. M.,58 156 Silver J. 225 285 Silver M. E. 173 220 Silvester D. J. 331 Author Index Silvestri A. 100 Sima P. D. 221 Simeon V. J. 288 Simhon E. D. 127 179 194 224 225 Simmons C. J. 99 283 Simmons K. 17 Simolo K. P. 215 Simon A. 187 31 1 Simon B. 186 Simon J. 298 Simon R. M. 5 Simon W. 11 Simopoulos A.127 224 225 Simpson J. 233 Simpson M. B. 146 200 239 Simpson S. J. 229 249 Sims H. E. 329 Sinclair G. R. 285 Sindorf D. W. 96 Singh A, 9 42 91 Singh P. 316 Singh P. P. 301 Singh S. 61 Singh V. P. 301 Singleton E. 230 Sinisterra J. V. 68 Sinn E. 49 57 130 181 214 235 237 282 285 Sinnreich J. S. 327 Sinoussi F. 183 Siray M. 80 Sirina T. P. 67 Sirokman F. 330 Sironi A. 204 251 254 258 287 296 Sita L. R. 99 Sjoeberg S. 62 332 Skelton B. W. 240 246 251. 262 275 290 294 297 Skibsted L. H. 294 Skjemstad J. O. 96 Skolozdra R. V. 315 Skotland T. 288 Skoweranda J. 281 Skvortsov V. G. 22 Slade M. J. 9 91 Sladky F. 158 Slater I. D. 292 Slater J. B. 335 Sletten J. 280 Sliwinski J.301 Slobodin B. V. 67 Slovokhotov Ya L. 266 302 Slovyanskikh V. K. 319 Small R. W. H. 75 296 Smid J. 14 Smirnov I. A. 3 12 Smirnov V. A. 71 Smirnyagina N. N. 73 Smith A. J. 320 Smith A. K. 263 Smith A. R. P. 282 Smith B. J. 200 Smith D. 238 Smith D. D. 338 Smith D. E. 233 Smith D. O. 243 259 Smith D. O’N. 28 Smith D. S. 168 Smith E. G. 214 Smith G. 17 245 Smith J. 12 285 Smith J. D. 6 90 107 Smith J. M. A. 129 186 192 Smith K. M. 219 222 Smith P. M. 327 Smith R. T. 261 Smith T. D. 285 Smyth J. R. 67 Smyth R. D. 337 Snaith R.,4 27 Sneddon L. G.. 38 47 48 49 50 Snow M. R. 199 237 Sobolev B. P. 311 Soeda Y. 65 Soenarjo S. 337 Sohn D. 332 Sokolov V. I. 266 302 Sokolovsky M.298 Solans J. 10 Solans X. 10 100 297 Soldinova J. 283 Soldo D. 71 Solenchek D. 337 Solntsev K. A. 50 Solodovnikov S. P. 154 Soloev Yu. I. 19 Solomon E. I. 296 Soloveichik G. L. 317 Solov’ev N. E. 19 Somack R. 337 Somer M. 125 Song L. C. 302 Songyue Yuan 309 Sonoda N. 232 Sood S. 146 333 Sootoo C. K. 107 Sorenson J. R.J. 288 Sorokin I. D. 167 Sorokin P. P. 150 Sorokina 0. V. 73 Sorrell T. N. 276 Sosinsky B. A. 227 296 Souchu A. 337 Sougchun Jin 3 17 Southern T. G. 132 Sova T. 261 Sowerby D. B. 114 11 5 156 Soye C. 320 Spahiu K. 322 Spalding L. 315 Spaulding L. P. 17 Specht S. 325 Speier G. 275 Speiser A. G. 335 Spek A. L. 6 280 284 297 Spence J. T. 182 Spencer C.B. 43 297 Spencer C. M.,262 Spencer R. P. 334 Speranza M. 330 Speridonov F. M. 3 11 Spicer L. D. 339 Spiering H. 218 Spiess M. 276 Spille H. 314 Spiridonov V. P. 144 155 Spirlet J. C. 318 319 329 Spirlet M. R.,324 Spiro T. G. 224 298 Spitsyn V. I. 146 308 325 335 Spitznagel G. W. 36 Spitznagle L. A. 333 335 Spliethoff B. 5 Sprague J. 18 Spratt T. E. 299 Springborg J. 237 Springer C. S. jun. 316 Springer J. P. 227 Sprinkle C. R. 132 138 264 Srinivasan S. 326 Srivastava P. G.,26 Srivastava R. C. 270 Srivastava S. C. 329 336 Srivastava T. S. 287 288 Stadlbauer J. M. 241 Stahl L. 249 Stahr 296 Stainer M. V. R. 316 Stalke D. 246 Stamicarbon B. V. 329 Stamouli M. I. 340 Stamp L.,276 Stanbury D.M. 216,250 Stanghellini P. L.,243 Stanic B. 73 Stanislowski A. G. 298 Starke U. 101 Stary J. 326 Stassis C. 305 Statalova G. E. 278 Staunton G. M. 318 Stedman G. 102 Steel A. 97 Steen N. D. C. T. 243 259 Steen R. J. 101 115 Steenstrup S. 308 Stefanac Z. 284 Stefanovich S. Yu. 306 Steffen R. 162 Steggerda J. J. 292 Steglich F. 314 Steidl G. 62 Stein L. 147 149 325 Stein P. 272 Steinberger B. 41 Steiner B. 331 Steinkruger F. J. 328 Steinmetz G. R.,263 Stelzer O. 268 Stemple P. 127 Stepanov N. N. 312 Stephan D. W. 126 225 Stephens F. S. 30 226 Stephens P. J. 222 Stephenson M. 245 Stephenson T. A. 249 252 256 264 Stem E. A. 214 Steurer W. 284 Stevens E.D. 220 278 Stevenson G. R. 8 Steward D. D. 346 Stewart C. A. 97 105 106 107 Stewart R. F. 23 Stibr B. 49 50 Stillman M. J. 300 Stinson A. J. 216 Stobart S. R.,95 Stocco G. C. 302 Stoddart J. F. 271 Stoecklin G. 328 333 334 337 Stone F. G. A. 51 56 175 199 200 228 243 246 247 253 260 271 292 294 Stone-Elander S. A. 331 Stoppioni P. 111 124 260 Storm C. B. 237 Storozhenko P. A. 61 Stoner W. 108 156 Straatmann M. G. 333 Strahle J. 164 294 Strand R. 298 Strand T. G. 155 Straub B. 251 Straughan B. T. 217 222 Strauss S.-H. 220 Streitwieser A. jun. 324 Strekachinskii. A. B. 31 1 Stremple P. P. 194 224 225 Strohmaier K. M. 237 Stromberg A. 133 Stronna L. 258 259 289 Strouse F.E. 222 270 Struchkov Yu. T. 58 266 279 285 301 302 Strumola D. D. 258 259 289 Stuart A. I. 106 Stufkens D. J. 226 Stuhl L. S. 237 Stumpf K. 33 Sturgeoff L. G. 187 Su C. H. 221 236 298 SuBrez C. B. 306 Subramanian P. 186 Subramanian S. 296 Subrtova V. 39 52 Sudheendra Rao M. N. 121 158 Sudmeijer O. 96 Sudnick D. R.,316 Sudo T. 61 Suekane M. 312 Sugasaka K. 341 Sugasawa H. 340 Sughara K. 242 Sugimoto T. 299 Sugisawa H. 84 Sugita M. 3 13 Sugiura Y. 215 Suglobov D. N. 322 Sukharevskii B. Ya. 278 Sukhoverkhov V. F. 144 Suleimanov G. Z. 59 Sulfab Y. 238 Sullivan A. C. 6 90 Sullivan B. P. 250 Sullivan J. C. 261 321 Summers R. 193 Sundaram P. M. 108 Sundberg M. 280 Sundermeyer W.158 Sundoro-Wu B. 331 Sundvall B. 115 Sunkel K. 22 Surat L. L. 67 Suryanarayana D. 281 Suslick K. S. 207 222 Sutcliffe R. 292 Sutin N. 234 235 Sutton B. M, 294 Sutton E. E. 252 Suzuki A. 341 Suzuki K. 328 332 Suzuki N. 65 Suzuki S. 321 Suzuki T. 296 313 327 Svaerd H. 332 Svajlenova O. 284 Svensson C. 71 117 166 318 hestka M. 302 Svitsyn R. A. 59 Svoboda K. 326 329 332 Swanson B. I. 261 Swanson R. 298 Sweeney W. V. 224 Sweigart D. A. 220 Swenson D. 127 224 Swepston P. N. 130 240 241 Swift C. A. 41 Swindells D. C. N. 114 151 Swiridofi W. 34 273 Swisher R. G. 49,99 181 Switendick A. C. 305 Switzer J. A, 235 Syad-Mustaffa B. 292 Syed-Mustaffa S. N. A. B. 253 Sykes A. G.288 Sylva R. L. 3 307 321 Symons M. C. R. 35 226 230 Syrota A. 331 332 Szalda D. J. 235 Author Index Szeymies D. 177 Szostak R. 270 Szuecs M. 330 Szymanska J. A. 300 Szymanska-Zachara E,,64 Tachikawa E. 338 Tachiki M. 312 Tadj F. 229 Tagesson B. 275 Tajik M. 323 Tajmir-Riahi H.A. 297 Takagi N. 341 Takahashi H.,68 341 Takahashi N. 337 Takahashi T. 190 333 Takahashi Y. 326 Takahashio M. 237 Takai N. 341 Takashima Y. 219 326 Takats J. 316 Takaya H. 172 Takayasu O. 326 Takemoto T. 215 Takeshita T. 309 Takeuchi E. 70 Takeuchi K. J. 241 286 327 Takeuchi T. 326 Taki K. 331 Tamai S. 220 Tamai Y. 68 Tamaki A. 3 13 Tamate K. 332 Tamaura Y. 211 Tarnburello A. 302 Tamerat G.31 1 Tamura H. 15 Tanabe T. 326 Tanaka H. 215,287,333 Tanaka K. 66 195 276 Tanaka M. 216,242 Tanaka N. 8 Tanaka S. 327 Tanaka T. 195,287 Tang L. C. 8 Tang T. W. 264 Tang Y. 338 Tang Y. N. 338 Tang Y. S. 331 Tanner P. A. 320 Tarafder M. T. H. 166 Tarantelli T. 213 280 Tarascon J.-M. 313 314 Tarasconi P. 100 Tarasov B. P. 43 Tarasov V. P.,307 Tarien E. 63 Tariverdian P.A. 291 Tarquini M. E. 172 Tashtoush H. 301 Tasker P. A. 298 Tasker R. F. 237 Tassot P. 67 Tatarowski T. 279 Author Index 395 Tatz R. J. 196 Tiekink E. R. T. 115 Trots S. V. 307 Taube H. 250,256 Tilbury R. S. 332 Trotter J. 30 31 32 100 Tauchmanova H. 332 Tautz H. 113 Taylor D. 237 Taylor H. 285 Taylor J. C. 161 318 323 Taylor J.G. 51 265 Taylor L. T. 130 203 Taylor M. R. 296 Taylor N. J. 243 248 289 302 Tilley T. D. 317 Timakov A. A. 162 Timmers D. 232 Timney J. A. 207 Timofeev G. A. 343 Tiripicchio A. 243 246 264 Tiripicchio Camellini M.,292 Tobita H. 82 83 84 277 279 283 292 302 TO,K.-C. 146 Troup J. M. 157 Troutner D. E. 335 Trueblood K. N. 3 Trumper J. 328 Truppat R. 28 Truter M. R. 17 75 Trynda L. 285 Tsai D. II. S. 25 Tsao Y. 235 Tse J. S. 147 Taylor P. 114 151 Taylor T. G. 299 Tazawa S. 329 Tocher D. A. 249 256 Todd L. J. 39 Todorovski D. 339 Tsekhanskii R. S. 22 Tsetskhladze J. V.,338 Tsibakhashvili N. Ya. 338 Tcheou F. 315 Totsch W. 158 Tso C. C. 261 Tebbe K. F. 92 110 Teitelbaum Z. 337 Toivonen J. 320 Tollefson N. M.,58 Tsuboyama S. 281 287 Tsuchiya S. 15 124 Teixidor F.57 296 297 Tolsma L. D. 307 Tsuge A. 237 Tempest P. A. 319 Templeton D. H. 43 172 Templeton J. L. 189 Ten Hoedt. R. W. M. 284 Toma H. E. 216 Tomas M.,207 250 Tomassen H. P. M.,14 Tomat G. 3 17 322 Tsukerblat B. S. 212 Tsukuma K. 327 Tsunekawa K. 65 Tsutsui M. 112 Teo B.-K. 194 225,258 Teo S.-B. 280 Tomer K. B. 102 Tomilov N. P.,63 Tsutsumi K. 68 Tsvetkov V. G. 22 Teoh S.-G. 280 Terai T. 326 Tominaga T. 338 340 Tomlinson A. A. G. 282 Tsybul’skii E. O. 278 Tuchagues J. P. M. 214 Tesmer T. 326 Tomor K. 61 Tuck D. G. 166 319 Tetrick S. M. 206 Tomura K. 338 Tucker J. R. 232 Thakur M.L. 329 Tondello E. 240 Tuenge R. T. 306 Thalken L. 212 Thambythurai A. 298 Thanedar S. 173 Tongson L. L. 69 Top S. 202 Toriumi K. 274 Turf& J. W. 164 203 Turkhima E. Yu. 75 Turnbull M.M.,11 1 Theis M.5 Theisen F.-J. 103 Theophanides T. 17 288 Torizuka K. 333 Torny G. J. 13 14 Toropova M. A. 325 Turner A. H. 237 Turner J. J. 146 200 207 239 Theopold K. H. 233 Therain F. 337 Torstenfelt B. 342 Toscano P. J. 237 Turss J. 10 Turunen M. J. 68 Thevet F. 71 Tosik A. 283 Tyagi S. 22 282 283 Thewalt U. 68 114 173 Toth G. 330 Tyler D. R. 232 Thiele G. 10 274 301 Touboul M.,23 24 74 Thom V. J. 285 Touhara H. 169 Ueda T. 262 Thom K. L. 82 TournC C. M. 183 Ueno A. 229 Thomas J. M. 63 68 81 96 TournC G. F. 183 Ueno K. 169 168 Toy A. 128 Ueno M. 17 Thomas J. O. 4 Trainor G. 229 Ueyama N. 235 Thomas K. E. 328 Traldi P. 112 Ugai Ya. A. 19 Thomas M. 119 123 125 Trampisch H. 175 Uggla R. 280 291 296 297 Thomas M. J. 228 Trankel R. B. 126 Tranov V.K. 165 Ugo R. 163 Uhl G. 106 Thomas P. L. 276 Traub W. A. 149 Uhlenhut G. J. 329 Thomas R. 297 Trautwein A. 192 193 Uhler A. D. 114 229 Thompson B. T. 68 Thompson J. S. 276 Thompson L. K. 283 Thompson R. C. 279 Thorez A. 132 Traverso O. 287 Traylor T. G. 219 Trefonas L. M.,278 Treichel P. M. 231 Tremmel J. 88 Ulman A. 241 Umezawa Y. 341 Ummat P. K. 301 Umreiko D. S. 320 Underhill A. E. 274 Thornback K. R. 284 Tressaud A. 164 Ungar R. K. 261 Thorne A. J. 97 Tricca R. E. 338 Urban G. 22 Thornton-Pett M. 208 209 Trigunayat G. C. 299 Urbannyk A. 176 243 245 Thrasher J. S. 161 Tichy K. 308 Tidor B. 5 Trobak N. 288 Trogler W. C. 180 270 Trogu E. F. 137 138 223 Trooster J. M. 294 Urch D. S. 339 Usatov A. V. 58 Uschkoreit J. 330 Ush A,. 295 Ush R.75 289 291 292 293 295 Ustynyuk Yu. A. 59 Usyatinskii A. Ya. 48 59 Utsunomiya K. 326 Vaalburg W. 327 332 Vacca A. 282 Vanngird T. 203 Vaeyrynen T. 335 Vagg R. S. 30 Vaida J. 226 Vajda P. 308 Valencich T. 338 Valent A. 284 Valente E. J. 161 Valentini G. 261 Valeri C. R. 336 Vallabhajosula S. 330 Valle G. 216 291 317 Val’tsev V. K. 313 van Brecht B. J. 166 van Buuren G. N. 95 245 253 Vance C. T. 199 Vanclef A. 144 Vandecasteele C. 33 1 Vande Griend L. 155 156 van den Driessche R. 336 van den Winkel P. 336 Van der Daes L. 333 van der Helm D. 93 100 van der Kerk G. J. M. 20 van der Kerk S. M. 20 van der Kerk-van Hoof A. 20 van der Ley M. 339 Van der Pers N. M. 68 Van Derveer D.243 Vanderveer M. C. 192 van der Velden J. E. A. 292 294 van der Wed J. F. 332 Vandewalle T. 331 van Duyneveldt A. J. 281 van Eldik R. 238 Van Engen D. 276 Van Halteren B. W. 334 339 340 van Haven D. 331 Van Hest J. A. M. 283 Van Kasteren P. H. G. 96 van Koningsveld H. 295 van Koten G. 7 242 297 van Lier J. E. 205 334 van Linden J. G. M. 292 Van Poucke L. C. 291 Vanryckeghem W. 336 van Stein C. C. 297 van Vliet M. R. P. 297 Van Zee R. J. 305 van Zen A. 13 14 Vargas M. D. 248 254 292 Varghese J. N. 282 Vasaros L. 144 337 341 Vattis D. K. 252 Vaughn J. W. 186 190 Vecchi E. 112 Veenboer J. Th. 338 340 Veith M. 97 Vekris J. E. 114 151 Velapoldi R. A. 283 Vel’mizov S. L. 311 Velthuizen W.C. 278 Venanzi L. M. 263 270 289 Venkatasubramanian V. 12 Venkateswarlu K. S. 165 Verain A. 330 Verani G. 256 Verdaguer M. 230 Verheijdt P. L. 277 Verma R. D. 61 156 Vermeer P. 278 Vernois J. 328 Verschoor G. C. 71 281 284 300 Versloot P-C. 79 VCrtes A. 21 1 Vesinowski J. P. 150 Vettier C. 312 Viccaro P.J. 313 Vicente J. 100 293 295 Vidal J. L. 258 Vidal M. 336 Vierling F. 278 279 Vijayan M. 17 Vijayaraghavan R. 314 315 Vijverberg C. A. M. 9 Villacampa M. D. 295 Villinger A. 11 Vincent M. A. 107 Vining C. B. 306 Vinogradov A. A. 312 Viossat B. 320 Virin L. I. 62 Visentin G. 281 Vishnawath C. K. 17 Visser J. 339 Vitebskii I. M. 278 Vitulli G. 249 Vlaic K. 283 Vlasse M.20 297 315 Vlasse T. 283 Vogel M. 328 Vogler M. 169 Vogt M. 331 339 Vogt o.,314 Vogtle F. 11 12 13 Voitenkova E. K. 75 Vokhmin V. G. 308 Volkenshtein N. V. 305 Volkert W. A. 328 335 Volkov A. A. 342 Volkov V. V. 56 Vollert H. O. 150 Vollhardt K. P. C. 243 Volovkina T. E. 75 Volpe P. 338 Volz H. 284 Author Index von Ammon R. 342 von Bokkum H. 9 Von Dreele R. B. 279 von Itter F. A. 13 von Jouanne J. 21 von Plotho C. 29 Von Schnering H. G. 145 Voronkov M. G. 154 Vos G. 218 Voss E. 95 Vrachnou-Astra E. 177 Vrbaneich J. 229 Vrieze K. 297 Vroon H. 9 Vucina J. L. 335 Vuillemin L. 336 Wachter J. 194 308 313 Wade M. 240 Wade K. 4 27 37 38 Wade S. R. 295 Wadepohl H. 33 34 97 Waernes O.62 Wagenbach U. 331 Waghmore S. 339 Wagner C. T. 106 260 Wagner F. E. 115 Wagner G. 84 Wagner H. 279 Wagner K. 162 Wagner L. J. 230 Wagner M. P. 284 Wagner-Loeffler M. 337 Wahlgren U. 133 Wainwright K. P. 241 Waijon J. E. 149 Wakamori K. 308 Wakatsuki Y. 233 260 Walborsky E. C. 243 Walbrecht U. 140 Walker A. 267 284 Walker D. C. 241 343 Walker F. A. 221 Walker H. W. 243 Walker J. A. 52 53 54 262 Walker N. P. C. 99 Walkinshaw M. D. 256 Wall K. L. 194 Wallaart J. 330 Wallace F. A. 291 Wallace W. J. 323 Wallbridge M. G. H. 51 265 Wallis H. L. 102 Wallis R. C. 246 Wallwork S. C. 27 Walsh R. 153 Walters M. A. 219 Walther B. 266 Walton J. K. 294 Walton J. R.,216 Walton R.A. 206 207 256 272 291 Wanek P. M. 328 Wang H. H. 207 Author Index Wang P. M. C. 146 Wang S.-W. C. 298 Wang T. R. T. 336 Wang Z.-T. 57 Wani B. R. 165 Wannowius K. J. 284 Ward B. 241 Wardeska J. G. 237 Warkentin E. 167 31 1 Warner M. G. 102 154 Warnock G. F. P. 180 181 Waschenbach G. 73 Wasielewski M. R. 17 Wasserman. H. J. 201 324 Waszcyak J. V. 252 Watabe M. 231 Watanabe H. 82 Watanabe M. 9 Watanabe N. 169 Watanabe T. 205 Watanabe Y. 205 Watarai H. 298 Watarais H. 241 Waterfeld A. 80 157 161 Waters S.-L. 245 Watson A. D. 224 237 288 Watson W. H. 12 Watts O. 229 Watz L. 284 Waugh A. B. 161 176 318 Wayland B. B. 257 Weakley T. J. R. 115 Weatherill T.D. 179 Weaver J. H. 307 308 Weaver M. J. 216 315 Weber E. 15 Weber G. 13 Weber R.,256 Webster M. 273 Wedd A. G. 199 201 Wedemeyer H. 325 Wegman R. W. 232 Wehner W. 13 Weiblen B. J. 336 Weichmann J. 95 Weigel F. 3 11 Weigl F. 320 Weinberg E. L. 97 Weinreich R.,330 Weiss E. 6 Weiss J. 34 74 273 Weiss R. 176 190 284 Weitl F. L. 334 Weitz E. 226 Welch A. J. 22 51 56 242 260 27 1 294 Welch M. J. 331 333 334 Weller F. 165 178 186 204 Weller M. G. 286 Wellon G. C. 283 Wells C. F. 238 Wells P. B. 252 Welsh W. J. 330 Weltner W. jun. 305 Went M. J. 243 Wentrup C. 106 Wentworth R. A. D. 194 Wenzel M. 337 Wermer P. 226 Werner A. 314 Werner H. 263 271 Werner K. V. 275 Werner P.E. 70 284 309 Werner W. 267 Wertenbach H. 325 Weser U. 286 288 Wessely H. J. 106 West B. O. 127 223 West J. T. 221 West R. 82 83 94 Westall W. A. 3 10 3 1 1 Westland A. D. 166 Westrum E. F. jun. 308 Wheeler W. B. 333 Whelan T. 37 White A. H. 9 72 89 91 181 240 246 251 262 275 277 290 294 297 302 3 11 323 White A. L. 6 White C. 248 White D. K. 222 White P. S. 114 123 136 151 159 249 White S. K. 332 Whitehead G. 4 Whiteley M. W. 228 Whitmire K. H. 248 253 254 292 Whitmore B. C. 284 Whitney J. F. 276 Whittaker J. 287 Whittle R. R. 58 237 263 Whittlesey B. R. 103 198 Whitwell G.E. 128 Wiberg N. 84 Wicholas M. 285 Widenbruch M. 82 Wiebk L. I. 337 Wiedemeier H. 276 Wieghardt K.206 273 Wiegman T. 327 332 Wieland B. 332 Wiggins R. W. 177 Wild S. B. 302 Wilhelm D. 34 Wilhelm J. G. 342 Wilke G. 32 Wilkes J. S. 62 Wilkes L. M. 251 Wilkinson G. 208 209 243 256 Will G. 19 23 Willes M. J. 98 Willett R. D. 278 279 Willey G. R. 295 Williams D. J. 84 99 271 Williams D. M.,165 Williams D. R.,98 287 Williams G. A. 282 Williams G. D. 232 Williams G. M. 260 Williams H. D. 91 172 Williams J. M. 43 266 274 285 Williams K. D. 333 Williams M. L. 290 Williams R. D. 21 Williams R. J. P. 291 Williamson R. F. 163 175 226 Willis A. C. 95 198 253 Willis W. H. 329 Willner H. 152 Willner I. 15 Wilson D. R. 209 Wilson G. S. 130 236 282 Wilson I. 222 Wilson L. J. 137 223 236 Wilson P.D. 329 Wilson R. D. 22 102 147 154 Wilson S. R. 179 264 Wilson W. D. 16 140 145 147 148 Winfield J. M. 144 Wingfield J. N. 3 17 235 Winkelmann G. 216 Winkler J. R. 182 Winkler P-P. 301 Winter G.,115 Winter M. J. 202 Wippermann T. 108 Wiseman G. H. 93 Wishart J. F. 284 Wishnevsky V. 3 11 Wisian-Neilson P. 11 1 Withers A. S. 316 Withers H. P. 99 Witte E. G. 341 Witten E. H.,130 234 Wittig H. 7 Wittig K. 331 Wittke O. 283 Wittman K. 274 Wiygul F. M. 137 Wiza J. 337 Wlodarnyk A. 192 Wohlers H. D. 216 Woitzik M. A. 267 Wojakowski A. 320 Wojicki A. 228 Wold A. 132 Wolf A. P. 146 329 330 332 333 Wolf w. 333 335 337 Wolochowicz I. 186 Wolsey W. C. 51 271 Wong C.238 Wong C. M.,123 159 Wong C. S. 101 Wong E. H. 40 11 1 Wong G. €3.. 215 216 Wong K. S. 44 Yamashita H. 327 Wong R. J. 279 Yamashita M.,65 214 285 Wong W. 243 Yamatera H. 341 Wong-Ng W. 84 Yamauchi S.,340 Wood F. E. 269 Yamazaki H.,233 260 266 Woods B. A. 257 Yamazaki T. 332 Woods C. 261 Yanada Y. 15 Woodward P. 175 243 246 Yanchevskaya T. V. 61 260 292 Yang G. K. 242 Woodward R. B. 298 Yannopoulos A. 300 Woolum D. S. 326 Yano Y. 327 331 Worley S. D. 203 Yanovskii A. I. 52 Worrall I. J. 75 296 Yanovsky A. I. 285 Worthington P. 252 Yaraliev Ya. N. 143 Wrackmeyer B. 26 Yarmush D. M. 316 Wright A. 319 Yashima E. 187 Wright A. F. 321 Yashina N. I. 59 Wright J. R. 288 Yaslak S. 110 Wright M. E. 230 Yasufuku K.80 Wright P. A. 63 Yasui T. 17 72 Wright S. 240 Yatsimirski A. 163 Wright T. C. 97 104 198 Yatsimirskii K. B. 59 227 259 Yee E. L. 375 Wrighton M. S. 226 Yeh S. 166 318 Wu C. C. 227 Yellowlees L. J. 250 Wu C. H. 3 Yishinaga M. 15 Wu E. 338 Yokoi H. 284 Wu G. Q. 167 Yokoyama A. 330 335 Wu J. L. 337 Yokoyama Y. 333 Wu Y. 308 Yoneda H. 237,238 Wurthwein E-U. 3 5 Yonezawa T. 243 261 Wuest J-D. 99 Yongjian L. 328 Wulfe G. 26 Young C. G. 188 wutz w. 334 Yoshida M. 22 Wyatt J-L. 226 230 Yoshida T. 262 Wyatt R. S. 167 310 Yoshifuji M. 103 109 125 Yoshihara K. 340 Xiang S. F. 154 Yoshikawa Y. 281 Xie Z. M. 111 Yoshioka Y. 88 Xue F. 23 Youfeng H. 328 337 Young J. P. 166 319 Yachandra V. 298 Young R. 241 Yachandra V.K. 224 Youngs W. J. 262 268 Yagi M. 333 Yperman J. 291 Yagubski E. B. 276 Yu Y. F. 228 Yagupolskii L. M. 146 Yudin I. P. 326 Yagupolskii Yu. L. 302 Yuki H. 8 187 Yakobson G. G. 144 Yusa H. 327 Yalpani M. 26 32 Yusuff K. K. M. 278 Yamada H. 70 Yu-Tai J. 334 Yamada M. 65 Yamada W. I. 329 Zacharis H. M. 327 Yamagami S. 326 Zafiropoulos T. 68 Yamagishi A. 237 Zahner K. 340 Yamahachi Y. 62 Zaika D. 29 Yamakawa M. 172 Zaitsev V. M. 337 Yamamoto A. 271 Zaker A. M. 312 Yamamoto K. 333 Zakharkin L. I. 58 59 Yamamoto S. 332 Zakharov A. A. 69 Yamamoto Y. 65 260 266 Zakharova B. S. 66 Yamamura T. 195 225 Zalkin A. 43 91 172 317 Yamana Y. 321 Zambonelli L. 263 270 289 Yamaguchi T. 289 Zamboni R. 180 Yamasaki A. 237 Zanazzi P. F. 213 276 280 Yamasaki T.333 Zanchini C. 234 Author Index Zanella A. W. 239 Zanello P. 235 285 Zanirato P. 33 Zanobini F. 236 Zanoli A. F. 275 Zanotti G. 281 284 Zanzonico P. B. 327 Zaworotko M. J. 95 Zay I. 21 I Zebrowski J. P. 179 Zeer E. P. 161 318 Zehnder E-J. 299 Zeigler M. L. 260 Zel’tzer I. E. 285 Zeman A. 326 Zemskov S.V. 144 Zengerly T. 94 Zenneck U. 34 Zerner B. 214 Zewall M. A. 337 Zeyen C. M. E. 312 Zhang C. S.,149 Zhang J-H. 212 Zhao J. 23 Zhdanov A. A. 154 Zheng G-X. 57 Zheng L. 53 54 262 Zhigareva G. G. 59 Zhong-Yun P. 334 Zhu J-K. 25 118 119 285 Zhu N. J. 222 Zhu T. 236 Zhukov E. G. 76 Zhukova L. V. 73 Ziegler M. L. 92 106 113 Zil’berman B. D. 144 Zilm K.W. 82 Zimmer L. L. 216 Zimmerman G. J. 50 Zimmerman P. G. 276 Zinchenko R. V. 23 Zinn W. 311 312 Ziolo R. F. 157 Zisapel N. 298 Zobov V E. 161,318 Zocchi M. 249 Zoet R. 242 Zogal 0.J. 308 Zoghbi S. S. 329 Zonnevijlle F. 183 Zozulin A. J. 324 Zribi G. 313 Zsolnai L. 104 105 Zubieta J. 128 185 193 277 285 Zubieta J. A. 128 187 188 189 190 Zubov A. S. 67 Zubreichuk Z. P. 56 Zuckerman J. J. 93 100 Zuniga F. J.. 296 Zuman P.,28 Zutshi K. 28 Zybill C. 107 125 Zybill C. E. 138 212

ISSN:0260-1818    

DOI:10.1039/IC9838000365

出版商:RSC    

年代:1983

数据来源: RSC