ISSN:0260-1818    

DOI:10.1039/IC98986FX001

出版商:RSC    

年代:1989

数据来源: RSC

ISSN:0260-1818    

DOI:10.1039/IC98986BX003

出版商:RSC    

年代:1989

数据来源: RSC

摘要:

0,S Se Te By F. J. BERRY School of Chemistry University of Birmingham P.0. Box 363 Birmingham B 15 277 1 Introduction The usefulness of the Group VI elements in the preparation of technologically important inorganic materials has continued to dominate interests in this area of chemistry. Studies of the new generation of 'warm' superconductors illustrate this very well since preparative solid state inorganic chemistry is central to the improve- ment of methods for the synthesis of the materials and is crucial to the search for new ceramic high temperature superconductors. It is now appreciated that the initial synthetic routes which often involved the use of high temperatures to decompose the reactant mixed oxides have tended to give materials in which the particle size is difficult to control and are not well suited for the fabrication of samples suitable for electrical experiments.Hence it is relevant to note the publication this year by teams active in this field of research of simpler synthetic routes for the preparation of yttrium-barium-copper oxides which should assist future developments in the synthetic chemistry of high- T superconductors in particular and solid state inorganic chemistry in general. A solution route to precursors of yttrium-barium-copper oxides has been described.' This method involves either the hydrolysis of stoicheiometric mixtures of Y(OCHMe2)3 Ba(OCHMe2)3 and a hydrolysable copper compound such as Cu(OCMe3) in tetrahydrofuran by water or the precipitation of the metals from mixed nitrate solutions with aqueous Na2N202.The precursors were converted to the finely powdered 123 tetragonal polymorph by heating at 650-700 "C in argon and were transformed to the orthorhombic phase by heating in oxygen at 400°C. The higher members of the homologous series such as YBa2Cu403 and Y,Ba4Cu7OI5 which have previously been synthesized under oxygen pressure of 200 atmospheres have been prepared2 by heating stoicheiometric mixtures of nitrates at 750 "C under flowing oxygen and then heating the precursor with Na2C03 or K2C03 under oxygen for three days at 800°C. Other attempts to prepare YB~,CU~O,-~ have involved the use of the precursors BaCuO and Y,CuO to give single phase product^.^ Another new method for the synthesis of yttrium-barium-copper oxide has involved the mixing by spray-drying ' S.Horowitiz S. J. McLain A. W. Sleight J. D. Druliner P. L. Gai M. J. Vankavelaar J. L. Wagner D. B. Biggs and S. J. Poon Science 1989 243 66. R. J. Cava J. J. Kajewski W. F. Pock B. Botlogg L. W. Rupp R. M. Fleming A. C. W. P. James and P. Marsh Nature 1989 338 328. R.-H. Choy W.-Y. Choe and Q. W. Choi Mat. Rex Bull. 1989 24 867. 21 22 F. J. Berry techniques of aqueous solutions of ionic salt precursor^.^ The anions in the spray- dried mixtures appear to participate in a low temperature exothermic oxidation- reduction reaction which converts the precursors into their corresponding mixed oxides and gives the single phase YBa2Cu30,- product by subsequent treatment at 910 "C for 10 minutes.Superconducting oxides in the form of powders or coatings have also been synthesized' from aqueous metal ethylenediaminetetraacetic acid (EDTA) solutions which were ultrasonically dispersed and converted to an aerosol of very fine droplets in an oxygen carrier stream. The submicron size oxide particles were collected by passing the aerosol through a tubular high temperature furnace. Another method of preparing high purity thin films of complex metal oxides by aerosol processes and which is applicable to the formation of ferroelectric and ferrimagnetic solids as well as superconducting materials has been achieved6 by the regulated deposition of ceramic powders from a gas phase suspension. Thin films of yttrium-barium-copper-oxide YBa2C~307-6 have also been fabri- cated by organometallic chemical vapour deposition techniques7 using tetramethyl- heptanedione complexes as source materials.The interaction of YBa2Cu307- and Bi,Sr2CaCu20 with zirconia alumina magnesia and strontium titanate has been investigated at temperatures close to those used for the synthesis of the superconduct- ing phases with a view to selecting suitable materials for use as substrates for high-T superconducting films. The foregoing gives some indication of the type of synthetic chemical studies now in progress on high temperature superconductors. It is also interesting to note the contribution of chemistry to theoretical aspects of superconductor research. For example a chemical model for high-temperature superconductivity which involves a two-stage chemical resonance mechanism has been proposed.' In this model attention was directed to implications for materials other than the now familiar cuprates and using the 70 K LaNiO based superconductor as an example the difficulties in preparation and chemical instability were explained in terms of the involvement of low-valent Ni' as the effective intermediate valance state.The treatment was extended to lone-pair systems e.g. Bi"' *Bi" and a conclusion drawn that many elements can give rise to high-T superconductivity and since metal- anion-metal distances are required to be small for high- T superconductors some of the more interesting compounds might require preparations under high pressure conditions. Analysis of the oxygen content of superconducting oxides has also attracted interest.A method involving the volumetric determination of oxygen in YBa2Cu307- has been reported" to have a reproducibility error of only A8 * 0.001. Another reported method" involved the slow cooling (1 "C/min) in oxygen of a sample heated to 930 "C and subsequent reduction under hydrogen in a thermobalance. K. Kourtakis M. Robbins and P. K. Gallagher J. Solid State Chem. 1989 82 290. A. Pebler and R. G. Charles Mat. Res. Bull. 1989 24 1069. T. T. Kodas Angew. Chem. Int. Ed. EngL Adv. Mat. 1989 28 794. ' K. Kanehori N. Sugii and K. Miyauchi J. Solid State Chem. 1989 82 103. D. Kovocheva K. Petrov and P. Peshev Mat. Res. Bull. 1989 24 1295. C. H. L. Goodman Mat. Res. Bull. 1989 24 1049.10 K. Conder S. Rusiecki and E. Kaldis Mat. Res. Bull. 1989 24 581. 'I S. P. Gorg R. Venkatararnani and S. Mazumder Mat. Rex Bull. 1989 24 803. 0,S Se Te 23 The chemical diffusion of oxygen in high density polycrystalline YB~,CU~O,-~ has been studied' by thermogravimetric techniques in the temperature range 550 to 850 "C under an oxygen pressure of 1 to lo- atmospheres. The chemical diffusion coefficient was found to be strongly sensitive to the oxygen composition. The enthalpy of oxidation of YBa,Cu,O (5.97 d x d 6.94) has been measured directly by high temperature reaction calorimetry and the partial molar enthalpy of oxygen dissolving in the structure found to be constant over the whole composition range.I3 The behaviour supports structural models in which the change in speciation from x = 6 to x = 7 is very gradual with Cu+ and Cu3+ coexisting in concentrations which vary smoothly with composition.The reaction kinetics for oxygen uptake into partially substituted YBa,Cu30 has been in~estigated'~ in materials of the type YIP,La Ba2Cu30, YBa2Cuz 5Feo 50,and Yo 5Nao ,Ba,Cu,O,. The reaction kinetics were found to decrease strongly on substitution at the copper site but to vary only slightly when substitution occurred at the rare earth site. Infrared reflectance spectroscopy Raman scattering and X-ray photoelectron spectroscopy have been used'5 to study the atmospheric degradation of YBa2Cu307-6. The degradation reaction 2YBa,Cu307 + 3co2 -+ Y,BaCuO + 5CuO + 3BaC0 + 0.50 was shown to be strongly catalysed by water vapour and to involve the build up of carbonate species in a matter of hours at room temperature.The influence of the copper and oxygen valence states in YBa,Cu307 on stoicheiometry and the interaction of the compound with water has also been studied by X-ray photoelectron spectroscopy.16 Gas chromatography-mass spectrometry have been used'7 to analyse the oxygen evolved from YBa2C~30698 when it is dissolved in acid and the results interpreted in terms of some of the lattice oxygen being present as 0-or peroxide ions. The superconducting BiSrCaCu,O,( T 80-1 10 K) phase has been prepared by a novel sol-gel process using oxalate as the complexing agent.I8 High density single phases of BiSrCaCu,O and Bi,Sr,Ca,Cu,O have been prepared by annealing the amorphous precursors which were obtained by quenching from melts." The super- conducting and structural properties of the solid solution series Bi,-,Pb,Sr,Ca,_,Y,Cu,O where 0 d x S 1 have also been reported.,' The com- pound Bi 04Sr1 76Mg0 3oCuo 9o06has been synthesized and shown to undergo a 20 low (6 K) superconducting transition.21 The structural and superconducting (T -107 K) properties of Bi2Sr2(Mi- M~),Cu30 (M' = Ca Y; M" = Na Ca) including hydrided materials have also been described.,' Other studies which illustrate the '' K.Kishio K. Suzuki T. Hasegawa T. Yamamoto and K. Kitazawa J. Solid Stare Chem. 1989,82 192. l3 M. E. Parks A. Navrots:.y K. Mocala E. Takayama-Muromachi A. Jacobson and P. K. Davies J. Solid State Chem.1989 79 53. l4 B. E. Higgins and H. Oesterreicher Mar. Res. Bull. 1989 24,739. l5 R. G. Egdell W. R. Flavell and P. C. Hollamby J. Solid Stare Chem. 1989 79 238. 16 P. Salvador J. L. G. Fiesso J. Amodor C. Cascales and I. Rasines J. Solid Stare Chem. 1989 81 240. M. W. Shafer R. A. de Grout M. M. Plechaty G. J. Scilla B. L. Olson and E. I. Cooper Mar. Res. Bull. 1989 24 687. V. Slusarenko K. R. Thampi and J. Kiwi J. Solid State Chem. 1989 79 277. 19 H. Sato W. Zhu M. M. Miller T. Ishiguro A. I. Schindler and C. S. Calhoun J. Solid State Chem. 1989 79 146. 20 R. Retoux V. Caignaert J. Provost C. Michel M. Hervieu and B. Raveau J. Solid Stare Chem. 1989 79 157. W. Urland and F. Tietz Mar. Res. Bull. 1989 24 489. l2 M. G. Smith and H.Oesterreicher Mar. Res. Bull. 1989 24 1103. 24 F. J. Berry type of copper-containing superconducting compounds which have attracted recent interest include T1,,5Pbo.5CaSr2Cu20~3 (Y1-xCa,)Ba2Cu30624 Nd2-xThxC~025 Lal+xSr2-xCu205.5+~6 It must be emphasized that many other and GdBa2C~30x.27 variants of the copper-containing superconductors mentioned above have been examined and that the literature on this area of chemistry is considerable and not amenable to comprehensive review. As mentioned earlier non-copper containing superconducting oxides are also attracting attention. It is especially interesting to note the prediction2* that some layered perovskite-related Aurivillius-type phases which have strikingly similar structures to those of the Bi-Ca-Sr-Cu-0 and T1-Ca-Ba-Cu-0 superconductors might form a new class of superconductors.The report29 that the critical temperature for superconductivity in the cubic perovskite (Ba K)Bi03 system has been increased to 34 K demonstrates that oxides not containing copper but with two dimensional structural properties are worthy of attention. Hence it is clear that the current level of chemical activity in studies of the synthesis structural properties and reactivity of oxide superconductors remains high and is producing fundamental solid state chemical information which will doubtless encourage further work in related systems. 2 Oxygen The first successful time-resolved detection of singlet oxygen luminescence using pulse radiolysis techniques has been rep~rted.~' A very sensitive infrared emission spectrometer with very low excitation powers has been used3' to determine lo2 lifetimes directly from phosphorescence decay in various chlorine- bromine- or iodine-substituted perfluorinated solvents and the data used to assess the influence of heavy atom substituted solvents on radiationless deactivation.The electronic structure of ozone has been examined32 and Jahn-Teller effects in its photodissoci- ation identified. The reaction of titanium sulphur and sulphur monochloride has been found33 to give the compound Ti40( S2)&1 which contains an oxygen-centred tetranuclear flattened titanium tetrahedron as shown in Figure 1. It is interesting to note the synthesis34 and characterization of a soluble oxide inclusion complex of composition [CH3CN(VI2O:,)] that has some molecular analogy to solid microporous oxides such as zeolites which are well known for their ability to reversibly absorb small covalent molecules in a size- and shape-selective fashion.23 A. K. Ganguli K. S. Nanjundaswanny C. N. R. Rao A. Sequeira and H. Rajagopal Mat. Res. Bull. 1989 24 883. 24 E. M. McCarron M. K. Crawford and J. B. Parise J. Solid State Chem. 1989 78 192. 25 T. C. Huang P. W. Wang E. Moran A. I. Nazzal and J. B. Torrance Mat. Res. Bull. 1989 24 875. 26 D. M. De Leeuw C. A. H. A Mutsaers G. P. J. Geelen and C. Langereis J. Solid Sfate Chern. 1989 80 276. 27 H. Shibahara L. D. Marks S.4. Hwu and K. R. Poeppelmeier J. Solid Srafe Chern. 1989 79 194.28 K. A. Yee T. A. Albright D. Jung and M.-H. Whangbo Angew. Chem. Inf. Ed. Engl 1989 28 750. 29 N. L. Jones J. B. Parise R. B. Flippen and A. W. Sleight J. Solid State Chem. 1989 78 319. 30 A. A. Gorman I. Hamblett and E. J. Land J. Am. Chem. SOC.,1989 111 1876. 31 R. Schmidt J. Am. Chem. Soc. 1989 111 6983. 32 D. J. Tannor J. Am. Chem. Soc. 1989 111 2772. 33 F. A. Cotton X. Feng P. A. Kibola and R. A. Sandor J. Am. Chem. Soc. 1989 111 2148. 34 V. W. Day W. G. Klemperer and 0.M. Yaghi J. Am. Chem. Soc. 1989 111 5959. 0 S,Se Te Figure 1 Structure of Ti,O( S2)& (Reproduced by permission from J. Am. Chem. SOC.,1989 111 2150) 3 Sulphur The reaction of hydroxide ions with elemental sulphur (s,)in aprotic solvents has been shown35 to give the trisulphur anion radical S,' as the major product.The reaction stoicheiometry (eight -OH per three S8 to give eight S;) was found to be consistent with the results for the electrochemical reduction of s8 in dimethyl sulphoxide and acetonitrile. In continued studies of polychalcogenide synthesis in molten alkali metal polysulphide solvents two novel one-dimensional compounds containing Si-ligands have been formed from the K-Cu-S system.36 The understanding of solutions of sulphur in liquid ammonia continues to attract interest. In one report3' UV-visible spectroscopy was used to monitor the solubiliz- ation process of sulphur in liquid ammonia and the concentration of the species S3N-shown to proceed through a maximum and to be the precursor species of S4N-.The addition of ammonium chloride to ammonia was found to slow down the first steps of the solubilization whilst the opposite effect was found when alkali amide was added to ammonia. Another report3 described some Raman spectro- scopic investigations and photochemical observations of solutions of sulphur in liquid ammonia. The study of sulphur-nitrogen compounds remains a significant area of activity in sulphur chemistry. The addition of SCI, SOQ S02C12 or SeCI to liquid ammonia followed by Pt( PR3),Cl has been shown39 to give complexes of the type R(s2N2)(pR3)2 Pt(NS0)2(pR3)2 R[(HN),SOdPR3)2 and R(Se2N2)(PR3)2 respectively. The reaction of [S4N3]CI or [S3N2CI]CI in liquid ammonia with 35 M. Hojo and D.T. Sawyer Inorg. Chem. 1989 28 1201. 36 M. G. Kanotzidis and Y. Park J. Am. Chem. SOC.,1989 111 3767. 37 P. Dubois J. P. Lelieur and G. Lepoutre Znorg. Chem. 1989 28 195. 38 P. Dubois J. P. Lelieur and G. Lepoutre Znorg. Chem. 1989 28 2489. 39 1. P. Parkin A. M. 2.Slawin D. J. Williams and J. D. Woolins J. Chem. SOC.,Chem. Commun. 1989 1060. 26 F. J. Berry [PtC12(PR3),] or [(L-L')PdCl,Pd(L-L')] where (L-L') is a C-N ligand has been shown4' to give [Pt(S,N,)(PR,),] and [Pd(S,N,H)(L-L')] respectively. In some cases complexes containing S3N- ligands were also obtained. The N2S4 donor complex [Cu(L')I2+ where L' is 1,4,10,13,-tetrathia-7,16-diazacyclo-octadecane has been found4' to show a chemically reversible cop- per(II)/(r) couple at El/ -0.31V w FJF; (ferrocene/ferrocenium) whereas the methylated analogue [Cu( L2)I2+ where L2 is 7,16-dimethyl-l,4,10,13-tetrathia-7,16~ diazacyclo-octadecane shows a more anodic copper(Ir)/(I) couple at E,, + 0.06V us F,/F:.The differences in redox potential were related to the stereochemical features of the copper( 11) complexes the crystal structures of which were determined for [Cu( L1)I2+ and [Cu2(L2)( NCMe)2]2+. The dehalogenation of [S4N3]Cl and [S5N5]Cl by 4-phenyl-1,2,3,5-dithiadiazoledimer (PhmN) in acetonitrile has been found4 to be accompanied by novel ring contractions to give the compounds [PhCNSSN][ S3N2]Cl and [(PhmN),Cl][ S3N3]. Ab initio self-consistent field molecular orbital calculations have been used4 to examine novel stereoelectronic effects in linear R2S3N2 and cyclic XS3N2 systems.The compound 1,3,5-trithia-2,4,6- triazapentolenyl has been suggested4 as a likely candidate for the synthesis of conductive systems. The stable sulphur-nitrogen radical which is arranged in stacks in the solid state was obtained by a multistep synthesis and found to have weak S. -.S interactions between stacks but negligible interactions within the stack. The reaction of Pt(C,H,)(PPh,) with 1,5-E2N4S2 (E = Ph2P Me2NC) in acetonitrile has been shown4' to produce high yields of Pt(1,5-E2N4S2)(PPh3), in which the q2-S,S'bonding between platinum and the heterocyclic ligand is analogous to that found in T2-alkene-platinum complexes. The reaction of S4N402 with PtCl,(PMe,Ph) in liquid ammonia has been found46 to give the compound Pt(PMe2Ph),[ S2N3( SO2)(NH,)] which is the first example of a PtS2N3 ring system and which was shown to consist of a square planar platinum(r1) with a puckered PtS2N3 ring (Figure 2).The reaction of the polymer n(SnCl,S,N,) or the dimer (SnMe2S2N2) with chloride ions has been shown4' to produce salts of the SnC14S2N;- or SnMe2C1S2N anions respectively. X-ray structural determinations showed the anions to ,contain the five-membered SnS2N2 ring. Dimeric aryl- dithiadiazoles (RCNSSN)2 (R = Ph or p-ClC6H4) have been found48 to undergo nitrogen insertion into the S-S bonds and to form the corresponding dithiatriazine dimers when treated with atomic nitrogen which was generated in a cool direct current plasma. The alkyl derivatives (R = Me Pr or But) gave polymeric products whilst the dithiadiazolylium salts [RCNSSk]+X- (R = Ph or p-CIC6H4; X = I 40 C.A. O'Mahoney I. P. Parkin D. J. Williams and J. D. Woollins J. Chem. Soc, Dalton Trans. 1989 1179. 41 N. Atkinson A. J. Blake M. G. B. Drew G. Forsyth A. J. Lavery G. Reid and M. Schroder J. Chem. Soc. Chern. Comrnun. 1989 984. 42 A. J. Banister W. Clegg Z. V. Hauptman A. W. Luke and S. T. Wait J. Chem. Soc. Chern. Commun. 1989 351. 43 R. M. Bannister and H. S. Rzepa J. Cheni. SOC.,Dalton Trans. 1989 1609. 44 G. Wolmershauser and R. Johann Angew. Chem. Int. Ed. Engl. 1989 28 920. 4s T. Chivers K. S. Dhathathreyan and T. Ziegler J. Chern. SOC. Chem. Commun. 1989 86. 46 I. P. Parkin A. M. Z. Slawin D.J. Williams and J. D. Woollins J. Chem. SOC.,Chem. Commun. 1989 58. 47 T. Chivers J. Fait and K. J. Schmidt Inorg. Chem. 1989 28 3018. 48 A. J. Banister M. I. Hansford Z. V. Hauptman S. T. Wait and W. Clegg J. Chem. SOC.,Dalton Trans. 1989 1705. 0,S Se Te a Figure 2 The X-ray crystal structure of Pt(PMe2Ph),[S,N,(S0,)( NH,)] (Reproduced by permission from J. Chem. SOC.,Chem. Commun. 1989 58) Br CN or S3N3) reacted with the nitrogen plasma to give high yields of the respective dithiatriazine (RCN3S2),. The reaction of (Me3SiN)Ph2PN( Ph)C( NSiMe,) with sulphur dichloride has been shown49 to give the 1,3,2,4,6-thiaphosphatriazine Ph2P( Ph)CN,SCl which upon reduction with triphenyl antimony gives the corre- sponding thiaphosphatriazinyl radical [Ph2P( Ph)CN3S]'.The ESR spectrum recor- ded from the radical showed the spin distribution to be heavily localized over the (P)-N-S region of the ring. Skeletal scrambling in the 1,3-NSN-bridged 5-phenyl-l,3,2,4,6-dithiatriazine (PhCN,S,) has been studied by NMR spectros~opy.~~ A mechanism involving two simultaneous 1,3-nitrogen shift pathways via carbon and sulphur was proposed and supported by comparing the observed depletion/enrichment rates with those predic- ted by a model based on two sets of coupled first-order site exchanges. The molecular geometry of Me,SiNSNSiMe3 in the gas phase has been studied by electron diffrac- tion and the molecule shown to possess C2 symmetry with a distorted syn syn c~nformation.~' The crystal structure of 2,7,9,14-tetrakis( diethylamino)- 3,5,6,10,12,13-hexathia-1,8-diaza-2,4,7,9,11,14-hexaboratricyclo[9.3 .0.043s] tetra- decane was described during a study of the synthesis and characterization of mono- bi- and tri-cyclic boron-nitrogen-sulphur ring systems.52 Attempts to prepare novel compounds with layered structures have resulted in the identification of a new quaternary paramagnetic compound of composition MnGa2xCr,-2xS4 (0.75 < x < 0.9) with a layered Znln2S (1IIa)-type str~cture.~ Magic-angle spinning ,*PNMR spectra recorded from the solid binary phosphorus sulphides P,S,(n = 3,5,7,9 or 10) have been reported and the multiplicity of the 49 A.W. Cordes H. Koenig and R. T. Oakley J. Chem. SOC.,Chern. Commun. 1989 710. 50 K. T.Bestari R. T. Boere and R. T. Oakley J. Am. Chem. SOC.,1989 111 1579. " D. G. Anderson H. E. Robertson D. W. H. Rankin and J. D. Woollins J. Chem. SOC.,Dalton Trans. 1989 859. 52 A. Kendrick H. Noth B. Stalla and W. Storch J. Chem. SOC.,Dalton Trans. 1989 1311. 53 H. Haeuseler and W. Kwarteng-Acheampong Mat. Rex Bull. 1989 24 939. 28 F. J. Berry 31 P resonances correlated with the structural inequivalences revealed by X-ray diifra~tion.'~ The collapse of the PB parts of the 31P NMR spectra of a-tetraphos- phorus trisulphide isothiocyanates at room temperature has been associated with 14N relaxation effects as opposed to chemical exchange processes.55 Salts of the first dithiaphospholium cation have been isolated and characterized as aromatic deriva- tive~.~~ X-ray crystal structure of 1,3,2-benzodithiaphospholium tetra-The chloroaluminate showed a planar geometry for the cation with short P-S bonds and together with spectroscopic data were interpreted in terms of unique 3prr-3prr bonding across the S-P-S moiety.It is interesting to note the attention being given to metal phosphorus trisulphides and the report of a novel tetrathiafulvalene- MPS3 (M = Mn Cd) layered composite material.57 In these studies hydrated potassium intercalates M1-,PS3K2x(HZO)y (M = M Cd) which were derived from MPS3 lamellar materials were reacted with (TTF),( BF4)2in MeCN to yield lamellar composites in which the tetrathiafulvalene (lTF) species were intercalated between the Ml-,PS3 slabs. The synthetic approach is worthy of note since it suggests a strategy to develop a class of new materials merging the fields of layered inorganic materials and organic metals.Studies of the reactions of sulphur dioxide with photochemically generated polypyridyl complexes of chromium( 11) have shown5* that three reactions occur when Cr(NN):+ ions (NN = bpy phen and substituted analogues) are subjected to visible light from a laser pulse in solutions containing SO2in 1.OM H2S04. The quenching reaction produces Cr( NN):+ which subsequently undergoes back electron transfer but in the presence of millimolar concentrations of SO2 the predominant reaction is electron transfer between Cr( NN):' and SOz to give the transient SO species. The reaction between sulphur dioxide and dry trimethylamine oxide has been re-in~estigated~~ with the most reactive product (CH3),( H)NCH2S03 being structurally characterized and its iodine oxidation and Lewis acid chemistry being subjected to further examination.The He1 photoelectron spectra of gaseous com- plexes formed by sulphur dioxide with the electron donors trimethylamine triethyl- amine diethyl ether and diethyl sulphide have been recorded and interpreted.60 Kinetic and spectroscopic evidence has been presented for the formation and decomposition of iron( m)sulphur( IV) transients during the iron( 111) catalysed autoxidation of sulphur( IV) oxides in aqueous solution.6' Four different reaction steps were identified as possible stages relevant to acid rain formation. The crystal structure of zinc thiogallate of composition ZnGa,S4 which can be used as an infrared window has been redetermined6 and shown to involve a disordering of the zinc and gallium ions.Two ternary compounds of composition Li2SiS and Li4SiS4 have been identified in the lithium-silicon-sulphur system63 and 54 R. K. Harris P. J. Wilkes P. T. Wood and J. D. Woollins J. Chem. SOC.,Dalton Trans. 1989 809. 5s B. W. Tattershall J. Chem. SOC.,Chem. Commun. 1989 216. 56 N. Burford B. W. Royan A. Linden and T. S. Cameron Inorg. Chem. 1989 28 144. 57 P. Lacroix J. P. Audiere and R. Clement J. Chem. Soc. Chem. Commun. 1989 536. 58 C. A. Simmons A. Bakac and J. H. Espenson Znorg. Chem. 1989 28 581. 59 A. B. Burg Inorg. Chem. 1989 28 1295. 6o T. Pradeep K. S. Sreekanth M.S. Hegde and C. N. R. Rao J. Am. Chem. SOC.,1989 111 5058. 61 J. Kraft and R. van Eldik J. Chem. SOC. Chem. Commun. 1989 790. 62 G. B. Carpenter P. Wu Y.-M. Gao and A. Wold Mat. Rex Bull. 1989 24 1077. 63 B. T. Ahn and R. A. Huggins Mat. Res. Bull. 1989 24 889. 0,S Se Te 29 their lithium ionic conductivities associated with their crystal structures. A matrix infrared spectroscopy in solid argon of molecular SiS2 generated by a reaction of SiS with atomic sulphur has been performed to examine the bonding and structural properties of SiS. The structure of Sn(CH3),Br. C4H6N2S has been found to consist of trigonal-bipyramidal molecules held together in pairs by two N -Ha -Br hydrogen bonds and with the ligand bonded to the metal through the sulphur atom.65 The reaction of Na2S.9H20 with 1,1,2,2,-tetra(2,4,6-tri-isopropylphenyl)-l,2-dibromoditin in air has been found66 to yield the sterically hindered four-membered l-oxa-3-thia-2,4-distannetane ring which is a distorted rhombohedron containing distinct Sn-S and Sn-0 bonds whereas the same reagents react under anaerobic conditions to give the corresponding 173-dithia-2,4-distannetane.A three-membered 1-thia-2,3-distannirane was postulated as being the common intermediate in the two reactions. Powder X-ray diffraction has been to study chemically twinned phases in the PbS-rich region of the Ag,S-PbS-Bi2S3 system. Six structures were characterized and a new phase built up of galena-like slabs was identified. Molecular- size PbS species have been68 stabilized in the open-pore structure of zeolite Y and mordenite via ion exchange with Pb(I1) and subsequent treatment with H2S at 295 K.Detailed analysis of the lead L,,,-edge X-ray absorption data showed that intrazeolite Pb02(Oz)3 (0 = zeolite oxygen) species in zeolite Y react with H2S to form monomolecular S,Pb(O,) species which are anchored to the zeolite framework. The intrazeolite PbS phase appeared to be more ordered at high loading levels of lead in zeolite Y. The coordination of Pb(I1) and the structure of PbS in the mordenite host was less ordered but similar to that of the monomolecular species in zeolite Y. The structure of K2[Pb{S2C=C(CN),},].2 H20 has been determined69 and found to consist of one-dimensional [Pb(S2C=C(CN),},l2-anions stacked along the crystallographic b direction.The preparation of 5-methyl-1,3,2-benzodithiarsolium and 5-methyl- 1,3,2- benzodithiastibolium cations has been and the naphthalenic nature of the compounds associated with the presence of unique prr-p~bonding of sulphur to arsenic and antimony. The compound tetraphenylphosphonium tetraiodotrithiotriarsenate PPh4[ As3S314] has been prepared from the reaction of As2S3 PPh41 and HI in CH212 at 80 "C and the [As3S314]- ion found by X-ray crystallography to consist of an As3S3 ring in the chair c~nformation.~~ The structures of gaseous trifluoromethylsulphurane CH3SF3 and trifluoro(tri- fluoromethyl)sulphurane CF3SF3 have been determined by electron diffra~tion~~ and both molecules shown to adopt trigonal bipyramidal structures centred on the sulphur atom.Caesium fluoride activated by thermal decomposition of its 1 :1 64 H. Schnockel and R. Koppe J. Am. Chem. SOC.,1989 111 4583. 65 G. Valle A. S. Gonzalez U. Vettori and R. Ettorre J. Chem. SOC.,Dalton Trans. 1989 927. 66 P. Brown M. F. Mahon and K. C. Molloy J. Chem. SOC.,Chem. Commun. 1989 1621. 67 A. Skowron and R. J. D. Tilley J. Solid State Chem. 1989 78 84. K. Moller T. Bein N. Herron W. Mahler and Y. Wang Inorg. Chem. 1989 28 2914. 69 H.-U. Hummel and H. Meske J. Chem. SOC.,Dalton Trans. 1989 627. 70 N. Burford and B. W. Royan J. Chem. SOC.,Chem. Commun. 1989 19. 71 N. Burford and B. W. Royan J. Am. Chem. SOC.,1989 111 3746. 72 H. Sinning and U. Muller 2. Anorg.AIlg. Chem. 1989 568 49. 73 A. J. Downs G. S. McGrady E. A. Barnfield D. W. H. Rankin H. E. Robertson J. E. Boggs and K. D. Dobbs Inorg. Chem. 1989 28 3286. 30 F. J. Berry adduct with hexafluoroacetone or carbonyl fluorides has been shown74 to react with SF4 at room temperature and by using radiotracer experiments involving 18F and 3sS the occurrence of weakly adsorbed SF4 at the surface of activated CsF has been identified. Tetrathiafulvalene (TTF) and its derivatives continue to be the most investigated donors for the generation of organic metals and superconductors. Pressed polycrys- talline samples of p-(BEDT-TTF),13 have been found75 to exhibit bulk superconduc- tivity with an onset temperature of 9 K and with zero resistivity being observed at 3.2 K.The synthesis and structure of bis(ethylenedioxy)tetrathiafulvalene,which is the first oxygen-substituted tetrathiafulvalene has been rep~rted'~ which gives scope for checking whether oxygen radical cations have relevance to the new ceramic oxide superconductors. The compound bis( phenylethylenedithi0)-tetrathiafulvalene (BPhEDT-TTF) has been synthesized7' and some electrochemically prepared salts of the new ?r-donor have been described. Synchrotron radiation has been used to collect EXAFS data from a series of naturally occurring and synthetic tetrahedrite (Cu Ag),,(Cu Fe Zn Cd)2Sb4S13 minerals7' and the results interpreted in terms of the coordination environment of the various metals and preferentially occupied sites. The results complement crys- tallographic data by giving information about each element in sites occupied by more than one cation and demonstrate the value of multi-element EXAFS in the investigation of a chemically and structurally complex mineralogical system.Photodissociation collision-induced dissociation ion-molecule reactions and kinetics experiments have been used to study the series FeS:(n = 1-6) generated from sequential reactions of Fe+ with ethylene sulphide in the gas phase.79 Studies of iron-sulphur compounds with compositions relevant to interests in protein chemistry have continued. For example a new development of single-crystal ENDOR studies of an s7Fe-enriched iron-sulphur [Fe4S4I3+ cluster have been described." Studies of alternative spin states in synthetic analogues of [Fe4S4]+ clusters have continued" and the structure of (Et4N)3[ Fe,S,( S-o-C,H,SBu'),] con-taining a reduced cluster with a compressed tetragonal distortion have been described." The first examples of bridged Fe,S double cubanes have been pre- paredg2 by exploiting the site-specific substitution property of the previously reported single cubane cluster [Fe4S4( L.S3)C1I2- where L.S3 is 1,3,5-tris[4,6-dimethyl-3-mercaptophenyl thio]-2,4,6-tris( p-tolylthio) benzene.3- The clusters were examined by cyclic-and differential-pulse voltammetry to investigate electron-transfer coupling across sulphur-containing bridges of variable length.The occurrence of electrochemical carboxylation coupled with nitrite reduction catalysed by 74 K.W. Dixon and J. M. Winfield J. Chem. SOC.,Dalton Trans. 1989 937. 75 D. Schweitzer E. Gogu H. Grimm S. Kahlich and H. J. Keller Angew. Chem. Inf. Ed. Engl. Adv. Mater. 1989 28 953. 76 T. Suzuki H. Yamochi G. Srdanou K. Hinkelmann and F. Wudl J. Am. Chem. SOC.,1989,111,3108. 77 K. S. Varma J. Evans S. Edge A. E. Underhill G. Bojeson and J. Becher J. Chem. SOC.,Chem. Cornmun. 1989 257. 78 J. M. Charnock C. D. Garner R. A. D. Pattrick and D. J. Vaughan J. Solid State Chem. 1989,82 279. 79 T. J. MacMahon T. C. Jackson and B. S. Freiser J. Am. Chem. SOC.,1989 111 421. 80 G. Rius and B. Lamotte J. Am. Chem. SOC.,1989 111 2464. '*M. J. Carney G. C. Papaefthymiou R. B. Frankel and R. H. Holm Inorg. Chem. 1989 28 1497. 82 T. D. P. Stack M.J. Carney and R. H. Holm. J. Am. Chem. SOC.,1989 111 1670. 0,S Se Te 31 [Fe,S,( SPh),]’+ and [Mo2Fe6S8( SPh)9]3- has been in~estigated.~~ Double-cubane clusters with the ReFe3S4 core have been assembled during studies of the stability range of heterometal cubane-type clusters.84 The previously synthesized and struc- turally characterized cubane-type cores [VFe3S4I2+ and [MoFe3SJ3+ have been inserted into the semirigid trithiolate cavitand ligand LS3 (1,3,5-tris(4,6-dimethyl-3-mercaptophenyl)thio)-2,4,6-tris(p-tolylthio) benzenate3- with the identification of regiospecific reactions at a vanadium site similar to that in nitrogena~e.~~ Both [NBu;],[ MoFe3S4( SPh)3( o-02c6c14)]2 and [NBu:l2[Fe4S4( SPh)4]- modified glassy carbon electrodes have been foundg6 to catalyse the multielectron reduction of HOC2H,N3 to give HOC2H4NH2 N, N2H4 and NH in water.The preparation and spectroscopic characterization of metal-sulphur clusters such as R2(NH4)-[CU~SI 21 R2 [cU4s 121’CH3CN R2[ CU4s12,g 1 R2[ (s5)21 R2[Fe4S4Br41 R2[ Fe,S,Br2C12] R2[ Fe4S4C14] R2[Fe2S2C14] where R = PPh, and of [Fe( DMF)6]- [Fe2S2C14] by the simple reaction of metal salts with H2S has been described.87 Vibrational spectra and normal mode analysis for Fe2S2 protein analogues together with resonance Raman spectral studies of structural variations among adrenodoxin and ferrodoxin have been rep~rted.~’*~~ The reaction of (5H,14H-6,8,15,17-tetramethyldibenzo[ b i][ 1,4,8,1 lltetra- azacyc1otetradecinato)-iron(11) [Fe(tmdbtd)] with elemental sulphur under very mild conditions in tetrahydrofuran(THF) has been shown” to give quantitative formation of the corresponding p-sulphido complex [{Fe(tmdbtd)},( p-S)]-THF in which the macrocyclic ligand adopts a saddle shape.The reactions of the sulphur- bridged metal cluster complexes M3(CO),(p3-CO)(p3-S) where M = Fe Ru or Os with W(CO)6 and W(CO)5(PMe2Ph) in the presence of ultraviolet radiation has yielded” the new mixed-metal cluster complexes M,W(CO),,L( p3-S),where L is CO PMe2Ph and OS~W(CO)~~(PM~~P~)~(~~-S). The reaction of OS~(CO)~~(~,-S) with W(CO)5(PMe,Ph) in the presence of ultraviolet radiation gave the new mixed metal cluster complex OS,W(CO)~~(PM~~P~)(~~-S). The reaction of a range of transition -metal carbonyl anions [MI- with 2-chloro-l,3,2-dithiarsolane has been shown to resultg2 in the formation of the metalloarsines [M-AsSCH2CH2S] where M-is [Mo(CO)3(rl-C5H5)]- [W(C0)3(77-C5H5)1- [Fe(CO)2(r7-c,H5)1- [Mn(CO),]-or [Re(CO),]-.Studies of the kinetics and mechanism of the iron( IrI)-catalysed autoxidation of sulphur(IV) oxides have been developed by examining the complex formation reactions which occur between equated Fe(II1) and S(IV) oxides using techniques such as chromatography UV -vis and FTIR spectroscopy and stopped flow kinetics 83 K. Tanaka R. Wakita and T. Tanaka J. Am. Chem. Soc. 1989 111 2428. 84 S. Ciurli M. J. Carney R. H. Holm and G. C. Papaefthymiou Znorg. Chem. 1989 28 2696. 85 S. Ciurli and R. H. Holm Inorg. Chem. 1989 28 1685.86 K. Tanaka S. Uezumi and T. Tanaka J. Chem. Soc. Dalton Trans. 1989 1547. 87 A. Muller N. H. Schladerbeck E. Krickemeyer H. Bogge K. Schmitz E. Bill and A. X. Trautmein Z. Anorg. Allg. Chem. 1989 570 7. 88 S. Han R. S. Czernuszewicz and T. G. Spiro 1.Am. Chern. SOC.,1989 111 3496. 89 S. Han R. S. Czernuszewicz T. Kimura M. W. W. Adams and T. G. Spiro J. Am. Chem. Soc. 1989 111 3505. 90 P. Berno C. Floriani A. Chiesi-Villa and C. Guastini J. Chem. SOC.,Dalton Trans. 1989 551. 91 R. D. Adams J. E. Bobin P. Mathur K. Natarojan and J.-G. Wang Inorg. Chem. 1989 28 1440. 92 E. W. Abel S. R. Allen and B. Khandelwal 1.Chem. Soc. Dalton Trans. 1989 885. 32 F. J. Berry experiment^.^^,^^ Evidence was reported93 for the stepwise formation of 1:1 1 :2 and 1 :3 sulphito complexes depending on the pH and concentration of the S(IV) oxides used.The mono- bis- and tris(su1phito) complexes of Fe(rI1) were shown9 to undergo two successive redox reactions and produce Fe(rr) SOf ,and S202-. The mechanistic aspects of the decomposition reactions were related to the nature of the initial complexes. The solution chemistry of the green aqua ion of cuboidal mixed valence Mo4S? in [MO~S~(H~O)~~]~+ where the average oxidation state is 3.25 has been in~estigated~~ and the molybdenum/sulphido cluster shown to exhibit remarkable stability in acidic solutions p-toluenesulphonic acid (HPTS) and HClO,. In a subsequent the green sulphide-bridged Mo;" ion [Mo3S4( H20)9]+ was prepared by decomposition of the cuboidal [MO~S~(H~O)~~]~+ and found to exhibit a solution chemistry which is strikingly different from that of the previously studied red [Mo304( H20)9]4+.The sulphur-bridged incomplete cubane type aqua ion [MO~S,(H~O)~]~+ has been shown97 to react with metallic tin and with tin(1r) to give [(H20)9M03S4SnS4M03( H20)9]8+ and Mo,SnS,.( aq)6+ respectively. The aqua ion [Mo~S,(H~O)~]~+ was found to react with metallic iron nickel copper mercury and magnesium but not with the divalent ions of the metals. The diphos (Ph2PCzH4PPhz) complexes of the Mo,S:+ core with p-tolylimido dithiophosphate and carboxylate coligands have been prepared and ~haracterized.~~ Three new trinuclear molybdenum-containing clusters have been prepared and structurally ~haracterized.~~ The compounds Mo3(p3-S)(p-S),Cl,( PPh3)+ (H20)z.3THF and [Mo3(p3-S)(p-S)3Cl,(dmpe)3]C1-2MeOH were prepared by reacting Mo3S7C14 with the corresponding phosphine ligands at room temperature in THF.The formation of the compound W3S7Br4 was achieved by heating stoicheiometric quantities of the elements in sealed tubes and was shown by X-ray crystallography to adopt a trinuclear structure (Figure 3) which is isomorphous with Mo3S7C1,. Fenske-Hall molecular orbital calculations have been used"' to examine the electronically induced conformational changes which occur in high valent bimetallic chalcogen complexes of the type [CpML],(p-L) where M =Mo Re and L =S 0.A theoretical study of the bonding in sulphur- and oxygen-containing molybdenum species of general formula MoS,O;T (n =04)has discussed the types of bonds that are expected to develop between the central molybdenum atom and the ligand orbitals."' An investigationlo2 of the oxidative transformations of [MoOS812- has led to the characterization of the MO(VI) 0x0 disulphido complexes [Mo2O2S9I2- and [MO,O~S~,]~-as a solid mixture in the structure of (Et4N)2[Mo202S9.14].The oxidative coupling of (Et4N),[ gave the MO(VI) linear tetramer (Et4N)2[Mo404S,8] which on reaction with NiC12 in MeCN 93 J.Kraft and R. van Eldik Inorg. Chem. 1989 28 2297. 94 J. haft and R. van Eldik Inorg. Chem. 1989 28 2306. 95 B.-L. Ooi C. Sharp and A. G. Sykes J. Am. Chem. SOC.,1989 111 125. 96 B.-L. Ooi and A. G. Sykes Inorg. Chem. 1989 28 3799.97 H. Akashi and T. Shibahara Inorg. Chem. 1989 28 2906. 98 A. C. Lizano J. F. Richardson and M. E. Noble Inorg. Chem. 1989 28 1451. 99 F. A. Cotton P. A. Kibala M. Matusz C.S. McCaleb and R. B. W. Sandor Inorg. Chem. 1989,28,2623. 100 B. E. Bursten and R. H. Clayton Inorg. Chem. 1989 28 2846. 101 B. D. El-Issa A. A. M. Ah and H. Zanati Inorg. Chem. 1989 28 3297. 102 A. 1. Hadjikyriacou and D. Coucouvanis Inorg. Chem. 1989 28 2169. 0 S Se Te S(1) Figure 3 Structure of the W,S,Br4 molecule (Reproduced by permission from Inorg. Chem. 1989 28 2623) gave the new chloro derivative (Et4N)[Mo202S,C1] as a result of ligand exchange. The structure of 42- and 44-electron (P2M2(C0)4(p-E)2 butterfly complexes (M = Cr Mo W; E = S Se SR PR) and related compounds have been rationalized on the basis of EH-MO calculations.'03 The possible existence of cis/ trans conforma-tions of the Cp and CO ligands was analysed together with an assessment of M-M versus E-E bonding in the 42 electron species.The interconversion between isomers was considered and the electrochemical behaviours of the [Cp2M02( p-SR)2]o'2+ complexes investigated. The compound of composition MO~(C~H&)S which is the purple product in molybdenum-dithiol reactions has been shown'04 to adopt a novel molybdenum(v) dimer dithiolate structure (Figure 4). The photoresponse behaviour of the polycrystalline tetrahedral metal-cluster chalcogenides GaMo4S and ZnMo2Re2S has been attrib~ted''~ to the Mo d-d transition with n-type character.The compounds were found to give photoresponse in aqueous acidic and alkaline solutions in 12/1- and Fe(CN)2-/3- redox electrolyte. The hexanuclear tungsten complex octakis(p3-sulphido)hexakis(triethylphos-phine)hexatungsten of composition [w6&(PEt3)6j has been synthesizedlo6 from the reaction of magnesium metal with a trinuclear tungsten chloro sulphido cluster compound prepared from W6ClI2 elemental sulphur and triethylphosphine. The cluster skeleton (Figure 5) was found to consist of a regular octahedron of six tungsten atoms coordinated with p3-sulphido ligands on each triangular face and triethylphosphine as each metal vertex. The structure is almost identical to that of the molybdenum analogue. Differences in the electronic spectra and the one-electron- oxidation and reduction potentials were discussed in terms of the electronic levels of the w& framework which may be regarded as the cluster core of the unknown tungsten analogues of the Chevrel phase compounds.Interest in tungsten(v1) I03 M. El Khalifa F. Y. Petillon J.-Y. Saillard and J. Talarmin Inorg. Chem. 1989 28 3849. 104 T. R. Halbert and E. I. Stiefel Znorg. Chem. 1989 28 2501. 105 M. Parantharnan G. Aravarnudan and G. V. Subba Rao Mat. Res. Bull. 1989 24 931. 106 T. Saito A. Yoshikawa T. Yarnagata H. Imoto and K. Unoura Inorg. Chem.. 1989 28 3588. F. J. Berry W Figure 5 Molecular structure of [W,S,( PEtJ6] (Reproduced by permission from Inorg. Chern. 1989 28 3588) tetrahalide oxides and chalcogenides is partially derived from their versatility as starting materials for synthesis but also reflects the curiosity concerning the diverse structural forms which they adopt.It is therefore interesting to note the synthesis of a new polymorph of tungsten(v1) sulphide tetrachloride WSCl, and its structural 0 S Se Te 35 characterization. lo7 The complex (p-ethylenediaminetetraacetato)(p-oxo)(p-sulphido)bis(oxotungstate(v)) has been preparedlog and shown by X-ray crystal- lography to be the first complex containing the W,(O),(p-O)(p-s)unit. New ternary Ln32Nb28Sgg (Ln = La Ce) compounds have been ~ynthesized'~' and the structure of La32Nb28S28 described as a mixed sandwich layered type in which the INbS21 and ILaSl slabs alternate.The origin of metal clustering in transition metal layers MX2 where M is a transition metal and X is chalcogen has been examined' lo by performing tight-binding band electronic structure calculations on CoMo2S4,V3S4 Mo2S3 and Nb2Se3. The energy factors governing the partial irreversibility of lithium intercalation in layered trichalcogenides MX3( M = Ti Zr Hf; X = S Se) and the structural changes in the intercalated species Li,MX3 have been assessed."' A one-step mechanism was proposed for chemical intercalation in which each metal of MX3 is affected by three lithium atoms at a time. The synthesis of a molecule containing a simple unsupported M-S-M' linkage has been described'12 in a report of the preparation and reactivity of the first structurally characterised heterobimetallic complex containing an unsupported bridging sulphur atom."2 The synthesis of the defect thiospinel systems Cul-,[Ti2]S4 by the extraction of copper from Cu[Ti],S4 with iodine at 45 "C has been de~cribed."~ Structural charac- terization of these metallic or semimetallic Pauli paramagnetic materials was achieved by use of X-ray- and neutron-diffraction.The open-circuit voltage of electrochemically lithiated Cu[Ti2]S4 was found to be higher than that of CU~,~~[T~~]S~. The preparation and physico-chemical properties of the new titanium(1v) porphyrin complexes (Por)Ti(Y,) where Y is S or Se and Por is porphyrinate dianion have been reported.' l4 The structure of the (TpTP)Ti( S,) complex where TpTP is tetrakis-p- toly( porphyrin) was solved by single crystal X-ray diffraction.The tantalum subsulphide of composition Ta3Sl, has been prepared115 by a sealed silica tube synthesis at 1300°C. The structure of the compound which is metallic at room temperature was shown to be closely related to that of Ta2S. A new barium tantalum sulphide of composition Ba3Ta2Sg has been prepared' l6 by sulphurization of a mixture of BaC03 and Ta205. Another phase of composition BaTa,S5 was prepared117 from the reaction of CS with a mixture of BaCO and Ta,OS and was found to be metallic and Pauli paramagnetic. Solid state reactions have been used'" to prepare two new chalcogenides of composition I(4Ta2Sll and K3Nb2Sell. The compounds contain the discrete anions Ta,S:i and Nb4Se6, which resemble the 107 F.A. Cotton P. A. Kibala and R. B. W. Sandor Inorg. Chem. 1989 28 2485. I08 S. Ikari Y. Sasaki and T. Ito Inorg. Chem. 1989 28 447. I09 A. Meerschant P. Rabu and J. Rouxel J. Solid State Chem. 1989 78 35. 110 E. Canadell A. LeBeuze M. A. El Khalifa R. Chevrel and M. H. Whangbo J. Am. Chem. Soc. 1989 11 3778. 111 E. Canadell C. Thieffry Y. Mathey and M.-H. Whangbo Inorg. Chem. 1989 28 3043. 112 J. A. Kovacs and R. G. Bergman J. Am. Chem. SOC.,1989 111 1131. 113 A. C. W. P. James J. B. Goodenough N. J. Clayden and P. M. Banks Mat. Res. Bull. 1989 24 143. 114 C. Ratti P. Richard A. Tabard and R. Guilard J. Chem. Soc. Chem. Commun. 1989 49. 115 H. Wada and M. Onoda Mat. Res. Buff.,1989 24 191. 116 M.Onoda and M. Saeki Mat. Res. Bull. 1989 24 625. 117 M. Saeki H. Nozaki and M. Onoda Mar. Rex Bull. 1989 24 851. 'I8 S. Schreiner L. E. Aleandri D. Kang and J. A. Ibers Inorg. Chem. 1989 28 392. F. J. Berry closely related tungsten and molybdenum species which can be prepared by solution methods. The reaction between (Cp*Ta)(SCH2CH2S), where Cp*Ta is pen- tamethylcyclopentadienyltantalum,with Li,S in tetrahydrofuran has been found’ l9 to give the compound [(Cp*Ta(S)3Li2(THF)2]2 which was shown to contain a hexagonal prismatic Ta,Li,S core (Figure 6). The compound [{Pr;P(CHz)3PPr~}TaHCl]2(p-S)(p-H)z has been prepared’” from the Na/Hg reduction of Ta,CI,( SMe,)3 in the presence of 1,3-bis(diisopropy1phosphino)pro-pane and was shown to contain a bridging sulphido ligand.Figure 7(a) shows that the sulphur atom bridges symmetry related tantalum atoms and although only one site occupied by the p-S is shown was found to occupy two locations each with 50% site occupancy. The side view [Figure 7(b)] depicts the likely positions of the bridging and terminal hydrides. Figure 6 Molecular structure of [(C,Me,)Ta(S)3Li2(thf)2]2 (Reproduced by permission from J. Am. Chem. Soc. 1989 111 782) Figure 7 (a) Molecular structure and (b) side view of [{PriP(CH2)3PPr;)TaHCl]2(p-S)(p-H)2 (Reproduced by permission from Inorg. Chem. 1989 28 1613) 119 K. Tatsumi Y. Inoue and A. Nakamura J. Am. Chem. SOC.,1989 111 782. 120 M. D. Fryzuk and D. H. McConville Inorg. Chem. 1989 28 1613. 0,S Se Te The magnetic structure of the compound PrCrOS has been examinedI2' and found to be antiferromagnetic and similar to other compounds of composition LnCrOX2 where Ln is La to Nd and X is S or Se.The metal carbonyls Mo(CO)~ and W(CO)6 have been found', to undergo oxidative decarbonylation in the presence of polysulphide or polyselenide to generate MSi- and MSei- respectively whilst the reaction of Cr(C0)6 with polysulphide solution generates the novel [(C,H5)4P]3[Cr(S2CO),1 complex in which the chromium is located in distorted octahedral sulphur coordination (Figure 8). The insertion of elemental sulphur into the cumulated linear triple bond Crr SesCr in [Cr,(Cp),(CO),Se] where Cp is r]-C5H5 has been found'23 to give [Cr,(Cp),(CO),Se,] [Cr2(Cp)2(CO)4S2]and [Cr2(Cp)2(CO)4S] together with the sulphur selenides S,Se and S,Se,.NMR and TLC studies indicated the transformation to occur via dichalcogen species of the type rcr,(cP),(co),s(se)l and [cr,(cp),(co),s(se>l. Figure 8 Structure of [Cr(S2C0),l3-(Reproducedby permission from Znorg. Chem. 1989 28 2780) Single crystals of the new semiconducting and diamagnetic phase Tl4Re6SI2 have been synthesized by high temperature reactions between TlX rhenium and sul- phur.l2 The anion [Ni,S(SC,H,),]- has been to contain a sulphide ion at the centre of a Ni6 prism capped by two additional nickel atoms in an arrangement involving nine p2-SBu' bridges (Figure 9). The anion is the first pure nickel-sulphur complex with nickel in the unusual mean oxidation state of +1.25.Complexes of the type (C,H4R)Ru(PPh3),EH where E is S or Se have been found to undergo condensation in hot toluene solutions to give compounds of composition [(C5H4R)4R~4E4] which contain the first Ru4E cubanes.'26 The synthesis and structural properties of the first closo and nido clusters of the type [(p-~ymene)~M~S,]'+ and [(p-~ymene),M,S,]~ where M is Ru or 0s have been repor- ted.', An optically active sulphoxide has been produced by using colloidally 121 M. Winterberger V. Tien M. Guittard and J. Dugue. J. Solid State Chem. 1989 79 285. 122 S. C. O'Neal and J. W. Kolis Znorg. Chem. 1989 28 2780. 123 L. Y. Goh J. Chem. SOC. Dalton Trans. 1989 431. 124 G. Huan M. Greaney P. P. Tsai and M. Greenblatt Znorg. Chem. 1989 28 2448.125 T. Kruger B. Krebs and G. Henkel Angew. Chem. Znt. Ed. Engl. 1989 28 61. 126 J. Amarasekera T. B. Rauchfuss and S. R. Wilson J. Chem. SOC.,Chem. Commun. 1989 14. 127 J. R. Lockemeyer T. B. Rauchfuss and A. L. Rheingold J. Am. Chem. Soc. 1989 111 5733. F. J Berry a U Figure 9 Schematic drawing of the Ni8S, framework of the complex anion [Ni,S(SC,H,),]-(Reproduced by permission from Angew. Chem. Znt. Ed. Engl. 1989 28 61) dispersed A-tris (2,2'-bipyridyl)ruthenium( 11) montmorillonite as a photo-sensitizer.I2' Novel dimers of composition [Rh(XB,,H,,){S,C( H)( PPh,)}] where X is Se or Te have been synthesized and shown to contain a unique cis-bis(phos- phonium-betaine) intercluster linkage with each ligand having one sulphur atom bridging both rhodium atoms and the other sulphur atom simply coordinating to a rhodium atom.'29 The first full assignment of the single-crystal Raman spectra between 275 and 1200cm-' recorded from the caesium rhodium alums CsRh(SO,),.12H20 CsRh( Se04)2.12H20 and CsRh(S0,),.12D20 at low tem- peratures has been rep~rted.'~' The crystal structures of [N(C2H,),][Pt{S2C,(CN),),1 and [H20],[NH,],~,[Pt{S2C2(CN)2}2]~2xH,0 have both been shown'31 to contain dimers. The dimer in the former species has a slipped configuration with Pt... S interactions whereas the latter contains the anion in an eclipsed configuration with a Pt over Pt arrangement. The electrical conduction and magnetic properties were related to the structures. The crystal structures of K[ Pd{S,C,(CN),},]~H,O and NH4[ Pd{ S,C,(CN),},].H,O have been described.'32 The former was found to adopt a structure consisting of an equidistant columnar stack of anions whereas the latter compound had anions arranged as dimers in an eclipsed Pd over Pd arrangement.The X-ray crystal structure of CS~.~,[ Pd{S2C2(CN),),].0.5H20 where S,C,(CN);- is 1,2-dicyanoethylene-1,2-dithiolate,has that the [Pd(S,C,(CN),},]-anions are strongly associated as eclipsed dimer pairs. The arrangement of the anion dimers (Figure 10) is unusual and leads to short S...S contacts between dimers in two orthogonal directions. A superstructure was observed at low temperatures and the structural properties of the material were related to its metallic conductivity when subjected to pressure.The interactions in dichloromethane solution of Pt(S,( NEt,) with a number of sulphur- and selenium-containing potentially biden- 128 T. Hikita K. Tamaru A. Yamagishi and T. Iwarnoto Inorg. Chem. 1989 28 2221. 129 Faridoon T. R. Spalding G. Ferguson J. D. Kennedy and X. L. R. Fontaine J. Chem. Soc. Chem. Commun. 1989 906. 130 S. P. Best J. K. Beattie R. S. Armstrong and E. P. Braithwaite J. Chem. Soc Dalton Trans. 1989 1771. 131 P. 1. Clemenson A. E. Underhill M. B. Hursthouse and R. L. Short J. Chem. Soc. Dalton Trans. 1989 61. 132 M. B. Hursthouse R. L. Short P. I. Clemenson and A. E. Underhill J. Chem. Soc. Dalton Trans. 1989 67. 133 M. B. Hursthouse R. L. Short P. 1. Clemenson and A. E. Underhill J. Chem. Soc.Dalton Trans. 1989. 1101. 0,S Se Te Figure 10 View along the b axis of CS~.~~[P~{S~C~(CN)~}~]*O.~H~O (Reproduced by permission from J. Chem. SOC.,Dalton Trans. 1989 1101) tate ligands have been studied'34 by multinuclear (31P 77Se 195Pt) magnetic resonance techniques and compared to the reactions of Pt(S,P{OEt}2)2. A new tetradentate macrocyclic ligand in which two amide and two sulphide units act co-operatively has been found135 to show high selectivity and efficiency for complex formation with platinum(I1) and palladium(I1) over copper(II) nickel( I]) and colbalt(r1). The synthesis of [Pt,(p-S)(p-dppm)( ~'-dppm)~] where dppm is Ph2PCH2PPh2 has been described'36 and its use for the formation of tetranuclear platinum complexes with p4-S ligands has been discussed.A study of the tetrathiafulvalenium salts of planar platinum( 11) palladium(II) and copper( 111) 1,2-dithio-oxalato-S,S' anions has the synthesis chemistry and molecular structures of bis(tetrathiafu1- valenium)bis( 1,2-dithio-oxalato-S,S')palladate(XI) [ttf12[ Pd( S2C202),] and of bis( tetrathiafulvalenium) tetrathiafulvalenebis( 1,2-dithio-oxalato-S S')platinate( II) [ttf13[Pt(S2C202)2]. The oxidation of the Pt2(p-S02)moiety to (p-SO3)has been rep~rted'~'and the crystal structure of [Pt2(p-S03)(p-S02)(CsH12)2)] has been described. The cyclopalladation reactions of several sulphur-containing ligands have been investigated and various examples of sulphur-assisted intramolecular pallada- tion of aryl and alkyl groups have been described."' Zinc sulphide films have been prepared by the conversion of zinc oxide films with hydrogen ~ulphide.'~' The films which contained both the hexagonal and cubic I34 R.Colton and J. Ebner Inorg. Chem. 1989 28 1559. 135 E. Kimura Y. Kurogi S. Wada and M. Shionoya J. Chem. SOC.,Chem. Commun. 1989 781. 136 N. Hadj-Bagheri and R. J. Puddephatt Inorg. Chem. 1989 28 2384. 137 C. Bellitto M. Bonamico V. Fares P. Imperatori and S. Patrizio J. Chem. SOC.,Dalton Trans. 1989,719. 138 D. H. Farrar and R. R. Gukathasan J. Chem. SOC.,Dalton Trans. 1989 557. 139 J. Dupont N. Beydoun and M. Pfeffer J. Chem. SOC.,Dalton Trans. 1989 1715. 140 Y.-M. Gao P. Wu J. Baglio K. Dwight and A. Wold Mar. Rex Bull. 1989 24 1215. 40 E J.Berry forms of zinc sulphide were shown to be uniform and gave a measured band gap of 3.65 eV. A new orthorhombic metastable form of cadmium sulphide CdS has been prepared through solid-gas reactions of CdO with a sulphiding gas mixture at 750°C for 3 hours and slow cooling under nitrogen atmo~phere.'~~ Controlled methods for the formation of cadmium polysulphide complexes from cadmium sulphide sodium sulphide and sulphur in DMF have been described.', '13Cd NMR was used to identify the existence of the series of monocadmium complexes [Cd(SX),l2- which undergo slow exchange (< 10 s-') at ambient temperature. The principal Cd NMR resonances were assigned to [Cd(S,),]'- [Cd(S,)(S6)I2- and [Cd(S6),I2- with [Cd(S,)(S,)]'- also being postulated. The crystal structures of (Ph,P),[Cd( s6),] and (Ph4P),[{(S6)056( S7)044}Cd( S6)] demonstrated the variability of cadmapolysulphane ring sizes and conformations which can be obtained within this sytem.The direct synthesis of cadmium sulphide within the pore structure of zeolites has been shown'43 to lead to a novel supercluster with a structural geometry superimposed by the host framework. Detailed X-ray powder diffraction and EXAFS analysis together with optical absorption data revealed discrete (CdS 0) cubes located within the small sodalite units of the structure which begin to interconnect as the loading density within the zeolite rises. The discrete cube building blocks were shown to consist of interlocking tetrahedra of cadmium and sulphur. At higher loadings the cubes begin to occupy adjacent sodalite units where the Cd atoms point toward each other through the double six-rings linking the sodalite moieties with a Cd-Cd distance of ca.6 A.The development of this three-dimensional interconnection is accompanied by corresponding changes in optical properties indicative of a progression towards a semiconductor supercluster with behaviour intermediate between that of the discrete CdS cubes and the bulk semiconductor. These types of semiconductor superclusters represent a novel class of materials where the three dimensional structure and electronic properties can be controlled by using different zeolites as the template. The unique stability of the semiconductor clusters inside the sodalite units derives from the coordination of cadmium atoms with the framework oxygen atoms of the double six-ring windows.The stability of the supercluster comes from the interaction between clusters in the adjacent sodalite units. Direct evidence for adduct formation between butenes and etched single crystal n-CdS and n-CdSe surfaces have been obtained from photoluminescence meas~rements.'~~ from three Infrared transmission spectra have been meas~red'~' kinds of spinel-type mixed systems Cd,Znl-xCr2Se4(1-,lS4Y where x = 1 y = 1 and x = y = 0.2 from 50-900 cm-' and at 300 and 16 K. Solid solutions throughout the whole composition range in the systems Y202S- La,O,S Y202S-Gd202S and Gd202S-La202S have been ~btained.',~ The electrical conductivity of the solid solution Eu~~Eu:',Li,-,S has been determined', by the 141 M.Kizilyalli M. Bilgin and A. Usuanmaz J. Solid Stare Chem. 1989 80 75. 142 R. M. Herath Banda I. G. Dance T. D. Bailey D. C. Craig and M. L. Scudder Inorg. Chem. 1989 28 1862. 143 N. Herron Y. Wang M. M. Eddy G. D. Stucky D. E. Cox K. Moller and T. Bein J. Am. Chem. SOC.,1989 111 530. 144 G. J. Meyer L. K. Leung J. C. Yu G. C. Lisensky and A. B. Ellis J. Am. Chem. SOC.,1989 111 5146. 145 K. Wakamura J. Solid State Chem. 1989 78 197. 146 C. R. Ronda H. Mulder and D. B. M. Klaassen J. Solid Sture Chem. 1989 80 299. I47 M. Palazzi and E. Bretey Mar. Res. Bull. 1989 24 695. 0 S Se Te complex impedance method and shown to be of electronic origin arising from electron transfer between Eu2+ and Eu3+.4 Selenium The anions in compounds of composition [(C2Hs)4N]2{ Se"Se'VBr8] have [(nC3H8)4N]2[Se~'Se'vBr,ol,and [(C6H5)4P]2[Se:'Se'VBr~2].cH2c12 been to contain distinct Se" and Se'" centres (Figure 11). The Se" centres in Figure 11 Sfrucrure of the [Se$e'"Br,,] anion (Reproduced by permission from Angew. Chem. Int. Ed. Engl 1989 28 187) these novel mixed valence compounds are coordinated in a square-planar fashion whilst the Se'" centres are octahedrally coordinated. The Se"-Se" distance of 3.335 is notably short. Compounds of the type (SkNSeNSk),(AsF,), where n is 1 or 2 which contain the first stable binary selenium-nitrogen species have been prepared by the reaction of stoicheiometric quantities of %4(ASF& (n = 2) or AsF (n = 1 and 2) with Se,N in liquid sulphur di0~ide.l~~ ESR spectroscopy showed that (deNSeNSk)2(AsF,) gives the indefinitely stable 7.n radical SeNSeNSe+' in solution whilst Raman and infrared spectroscopy showed that SeNSeNde( AsF,) gives the 67r SLNSeNSe2+ cation.The structures of the solid species were character- ized by X-ray crystallography. The reaction of Se4N with [PtCI2( PMe2Ph)12 in CHC13 has been found'50 to give Pt(Se3N)C1(PMe2PH) which is the first example of a metal selenium-nitrogen complex. The ccjmplex contains the bidentate selenium- bound Se,N- ligand and from X-ray crystallography was shown to be square planar with a bidentate Se,N- ligand coordinated through two selenium atoms. A more substantial interest in selenium-nitrogen chemistry might be a consequence of the synthesis'" of platinum complexes of the anions Se2Ni- and Se2N2H- in liquid ammonia which avoids the necessity to work with isolated unstable Se4N4.The method involves the addition of a complex such as cis-[PtC1,(Ph,PCH2PPh2)] to i? reaction solution of SeC1 in liquid ammonia and allowing the reaction mixture to 148 B. Krebs E. Luhrs F.-P. Ahlers Angew. Chem. Inr. Ed. Engl. 1989 28 187. I49 E. G. Awere J. Passmore P. S. White and T. Klapotke J. Chem. SOC.,Chem. Commun. 1989 1415. 150 P. F. Kelly A. M. Z. Slawin D. J. Williams and J. D. Woollins J. Chem. Soc. Chem. Commun. 1989 408. 151 P. F. Kelly I. P. Parkin A. M. Z. Slawin D. J. Williams and J. D. Woolins Angew. Chem. Inf. Ed. Eng. 1989 28 1047.42 F. J. Berry warm to room temperature to give selenium-nitrogen metallacycles such as [Pt(Se2N2)( Ph2PCH2CH2PPh2)] which can be protonated with HBF,. The X-ray structure of the related complex [Pt(Se2N2H)( PMe,Ph),]Cl showed the presence of essentially planar P2PtSe2N units stacked in a parallel and overlapping fashion. The reaction of (NSC1)3 with aluminium trichloride at 50 "C in the absence of solvent has been shown to produce [NS]+[AlCl,]- which reacts with alkylselenium halides to give [N2S2SeCl]+[A1C1,]- in which the cation is composed of a five-membered ring with chlorine attached ta selenium.'s2 The high-resolution 77Se NMR spectra of potassium and rubidium hydrogen selenities have been recorded using the cross-polarization method and the chemical shift tensors of selenium nuclei found to be typical for HSeO; c~nfiguration."~ The structure of the compound (Lao)@,,& 82 has been shown'54 to consist of alternating (Lao) and (Gao94Se2,41) layers parallel to the (001) plane.Studies of the soluble polychalcogenide chemistry of indium have been developed with the synthesis and characterization of [In,Se,,14- representing the first reported indium p~lyselenide.'~~ Single crystals of the new compound Pr,lnSe6 have been obtained'56 by direct reaction between Pr Se and ln,Se powders at 950 "C and were subjected to structural characterization by X-ray crystallography. The localized structural differences between crystalline and amorphous ger- manium diselenide GeSe2 have been examined by both Ge and Se K edge EXAFS and discussed in terms of clustering proces~es.'~~ The EXAFS recorded from ger- manium selenide glasses showed the selenium environment to vary strongly between GeSe3 and GeSe,,,.and between bulk phases and thin films as a result of selenium clustering in selenium-rich compositions.'s8 An X-ray crystallographic and dynamic 'H NMR study of 2,2,5,5-tetramethyl-1,3-diselena-2-germacyclohexane has shown's9 the compound to exist in a symmetrical 2,Stwist-boat conformation both in the solid state and in solution. The ,'P and 77Se NMR spectra of some sulphur- or arsenic-substituted derivatives of tetraphosphorus triselenide have been recorded16' and the chemical shifts and coupling constants fitted to molecular parameters for cage compounds containing a phosphorus-selenium-phosphorous linkage.16' Homonuclear dipolar coupling information derived from solid state NMR spectra have been used to test structural models of atomic distribution and local order in the phosphorus-selenium systern.l6' The reduction of As4Se by potassium in ethylenediamine in the presence of tetraphenylphosphonium bromide has been found'62 to form the compound P(C6H5)4*AS7Se4.The X-ray crystal structure showed the anion to contain arsenic 152 A.Apblett T. Chivers and J. F. Fait J. Chem. SOC.,Chem. Commun. 1989 1596. 153 I. S. Vinogradova A. A. Sukhovskii and F. F. Khizbullin J. Solid State Chem. 1989 78 209. 154 S. Benazeth P. Larnelle and M. Guittard J. Solid State Chem. 1989 78 148.155 M. G. Kanatzidis and S. Dhingra Inorg. Chem. 1989 28 2024. 156 L. E. Aleandri and J. A. Ibers J. Solid State Chem. 1989 79 107. 157 C. Peyroutou S. Peytavin M. Ribes and H. Dexpert J. Solid State Chem. 1989 82 70. 158 C. Peyroutou S. Peytou M. Ribes and H. Dexpert J. Solid State Chem. 1989,82 78. 159 S. Tomoda M. Shimoda M. Sanami Y.Takeuchi and Y. Litoka J. Chem. SOC.,Chem. Commun. 1989 1304. B. W. Tattershall R. Blachnik and M. P. Baldus J. Chem. SOC., 160 Dalton Trans. 1989 977. 161 R. Lathrop and H. Eckert J. Am. Chem. SOC.,1989 111 3536. V. Angilella H. Mercier and C. Belin J. Chem. SOC.,Chem. Commun. 1989 1654. 162 0 S Se Te Figure 12 Two views of the geometry of the As,Se anion in the compound P(C,H,),.As,Se (Keproduced by permission from J.Chem. SOC. Chem. Commun. 1989 1654) and selenium atoms in higher coordination than that which is generally observed in cage or cyclic anions involving arsenic and chalcogenide species. (Figure 12). The coordination of bismuth in dilute alloys of the noncrystalline Se,,,-,Bi system has been rein~estigated.',~ The synthesis of highly crystalline selenium analogues of sulphur-rich sulphur- iodine compounds Of the type Se6I,(ASF,)2*?SO, (Se61); nASF6 and (Se6I),*SbF6 has been des~ribed.'~~ The %,I:+ cation in Se612(AsF,)2-2S02 contains a six-membered ring of chair conformation with the two iodine atoms joined to the ring in the 1,4-positions with an endo conformation. Four intracationic I-Se contacts gives the cation a distorted cubelike shape (Figure 13).The geometry of the Se612 I Figure 13 The s~,I:+ cation in S~,I,(ASF,),.SO (Reproduced by permission from Inorg. Chem. 1989 28 3320) unit in the (Se61+), cations in isostructural (Se61);nMF6 (M = As Sb) is similar to that in Se,If' but the iodine atoms bridge Se rings giving rise to (Se61+), strands. (Figure 14). A short synthesis of tetraformyltetraselenafulvalene (TFTSeF) has been des- ~ribed.',~Its use as an efficient precursor of polyfunctionalized tetrasubstituted tetraselenafulvalene such as a tetravinylic derivative via a Wittig reaction and I63 A. Munoz F. L. Cumbrera and R. Marquez J. Solid State Chem. 1989 80 189. 164 W. A. Shantha Nandana J. Passmore P. S. White and C.-M.Wong rnorg. Chem. 1989 28 3320. 165 M. SallC A. Gorgues J.-M. Fabre K. Bechgaard M. Jubault and F. Texier J. Chem. SOC.,Chem. Commun. 1989 1520. F. J. Berry Selenium Iodine Figure 14 The (Se,I+),polymericchain in (Se,I);nMF (M = As Sb) illustrating the interaction of the bridging iodine atom with the adjacent Se rings (Reproduced by permission from Inorg. Chem. 1989 28 3320) tetrakis( hydroxymethy1)-TSeF by a simple NaBH reduction was demonstrated. The growth by anodic electrocrystallization of single crystals of the isomorphous electri- cally-conducting chloride and bromide of 1,4,5,8-tetraselenonaphthalene(TSeN) has been described.'66 The chloride was shown to be composed of dimers of parallel TeSeN cation radicals as opposed to infinite chains and to exhibit Curie law magnetic behaviour.The reaction of Cr(C0)6 with soluble polyselenide in DMF has been shown to result in complete oxidative decarbonylation and to give an unidentified mixture of higher chromium selenides.'22 The insertion of elemental sulphur into the linear triple bond CrESeGCr of [Cr,(~p),(C0)~Se] where cp is r]-C5H5 has resulted in the of [C~(cp),(C0)~Se,] together with other compounds including the sulphur selenides S,Se and S6Se2. X-ray diffraction and DTA studies of the pseudo- binary system Cr,VSe (0< x < 1) in the temperature range 300-1100°C have shown the existence of six phase^.'^' The thermal motion of silver in the two-dimensional silver ion conductor AgCrSez has been studied as a function of temperature by single-crystal X-ray diffraction.'68 The structural parameters superconducting critical temperatures and magnetic 166 L.A. Acampora B. S. Elman D. J. Sandman S. Jansen M. T. Jones R. D. Rotaiczak and B. M. Foxman Znorg. Chem. 1989 28 1579. 167 A. Hayashi Y. Ueda and K. Kosuge Mat. Res. Bull. 1989 24 825. 168 A. Van der Lee and G. A. Wiegers J. Solid Stare Chem. 1989 82 216. 0 S Se Te susceptibilities of the solid solution AgMo,S,- Sex have been reported and discussed in terms of structural and electronic instabilities in the AgMo,Se ~ystern.'~' The synthesis structure and properties of indium intercalation compounds of tungsten diselenide of composition Ln,WSe (0< x < 1) have been de~cribed.'~' The materials were found to exhibit n-type semiconductivity.The synthesis and structural properties of mixed metal selenide anions of composition Ni( Se,)( WSe,)'- and M(WSe,);- where M is Ni or Pd have been rep~rted.'~' The reaction of dimethyl acetylenedicarboxylate with WSei- and W,Se:; has been shown to give the new soluble anions of composition W(Se2C2(COOCH3),)~- and W2Se2( Se2C2(COOCH3)2)i- re~pective1y.l~' The origin of metal clustering in transi- tion metal layers has been examined"' by performing tight-binding band electronic structure calculations on a variety of metal sulphides and Nb2Se3. The electronic structures of butterfly complexes of the type P2M2(C0),E2 where M is Cr Mo or W and E is S or Se have been as~essed.''~ The new phase Tl,Re,Se, has been synthesized as single crystals from the high temperature reaction of TlSe selenium and ~henium''~ and shown to consist of Re6Se8 cluster units interconnected three-dimensionally by four selenium and two Se bridges (Figure 15).The compound is semiconducting and diamagnetic. W5) W5) ( Figure 15 Structural unit of Tl,Re,Se, (Reproduced by permission from Inorg. Chem. 1989 28 2448) The synthesis and structural properties of metal rich nickel cluster compounds with selenium ligands having novel structures have been de~cribed.'~~ The phase diagram of the (Fe,Ti,-,),Se system has been determined and the magnetic proper- ties e~arnined.'~ The 'H NMR and electron transfer properties of oxidized and reduced [Fe,Se,] derivatives of CZostridiurn vinosurn high-potential iron protein have been in~estigated.'~' 169 D.C. Johnson R. S. McLean and W. R. McKinnon J. Solid State Chem. 1989 82 35. 170 S. K. Sriovastava Mat. Res. Bull. 1989 24 1031. 171 M. A. Ansari C.-N. Chau C. H. Mahler and J. A. Ibers Znorg. Chem. 1989 28 650. 172 M. A. Ansari C. H. Mahler and J. A. Ibers Znorg. Chem. 1989 28 2669. 173 D. Fenske and A. Hollnagel Angew. Chem. Znt. Ed. Engl. 1989 28 1390. 174 A. Hayashi T. Kishi Y. Ueda and K. Kosuge Mat. Res. Bull. 1989 24 701. 175 M. Sola J. A. Cowan and H. B. Gray J. Am. Chem. Soc.; 1989 111 6627. F. J. Berry The synthesis of [ (Ph,P)AgSe,] and its characterization as the first silver poly- ~elenide'~~ is notable since it features an unprecedented low-dimensional polymer structure.The single-crystal X-ray diffraction analysis showed the material to be composed of non interacting Ph,P+ cations and [Ag( Se,)] :-macroanions which form infinite one-dimensional chains running parallel to the monoclinic b-axis (Figure 16). The basic repeating unit is a five-membered AgSe ring containing the chelating SeT2 ligand such that each chain can be envisaged as a corrugated ribbon. The structure is unique and has no parallel in chalcogenide chemistry. The pre- liminary examination of charge transport and optical properties along the needle axis indicated wide bandgap/narrow bandwidth semiconducting behaviour. Figure 16 Two views of a [Ag(Se4)]i-chain four unit cells long. Black dots represent silver atoms (Reproducedby permission from J.Am. Chem. SOC. 1989 111 760) Small ensembles of CdSe have been synthesized within the cage system of zeolite Y via ion exchange with cadmium(11) and subsequent treatment with H2Se.177 The cluster sizes and geometrical arrangements were determined by comprehensive analysis of Cd- and Se-edge EXAFS data and synchrotron X-ray powder diffraction data together with model calculations. The CdSe molecular clusters were stabilized at ambient conditions through strong interactions with the zeolite host. Se 0-bridged cadmium dimers and Cd404 cubes were identified in the sodalite unit. Cadmium ions present in 12-ring windows were found to be coordinated to one selenium and additional oxygen atoms. Small amounts of selenium helical chains and CdSe clusters were also detected.The photoluminescent properties of cadmium selenide in the presence of butenes have been reported.Ia The vibrational spectra of the spinel-type systems Cd,Zn,-xCr2Se4(l-,~S4 have been de~cribed.',~ The preparation of thin films of mercury selenide on a glass substrate has been achieved using mercury formamide and sodium selen~sulphate.'~~ The adherence and uniformity of the films was improved by addition of polyvinyl pyrollidone and the amorphous films found to be p-type semiconductors with an energy gap of 1.42 eV. 176 M. G. Kanatzidis and S.-P. Huang J. Am. Chem. SOC.,1989 111 760. I71 K. Moller M. M. Eddy G. D. Stucky N. Herron and T. Bein J. Am. Chem. SOC.,1989 111 2564. 178 P. Pramanik and S.Bhattacharya Mat. Res. Bull, 1989 24 945. 0,S Se Te 47 Vapour phase transport techniques using iodine have been to prepare single crystals of CeSel,9 and PrSe,, . An efficient one-pot synthetic procedure for the preparation of the electron donor bis( ethylenedise1eno)tretrathiafulvalenefrom tetrathiafulvalene has been described.'" 5 Tellurium The mixed oxides M2(GeTe)0 (M = K Rb Cs) have been prepared by a solid state reaction between Te(OH) ,GeO ,and MN03 and found to adopt a pyrochlore- type structure.'" The formation and thermal behaviour of glasses in the As-Ge-Te system has been investigated.'" Semimagnetic semiconductors with rare-earth mag- netic ions of the type Pb,-,Gd,Te have been prepared as single- and p~ly-crystals.'~~ The solid solution range was found to be limited to x < 0.1 and the gadolinium-lead ion substitution processes were discussed in terms of the NaC1-type structure.The EPR linewidths as a function of orientation temperature and composition were associated with relaxation mechanisms. Tellurium-125 NMR and electrochemical data recorded at mercury and platinum electrodes have shown'84 that the tellurium( IV) dithiocarbamate (dtc) complexes Te(dtc) are unstable in solution with respect to an internal redox reaction producing the tellurium(I1) complex Te(dtc) and thiuram disulphide with a rate which is solvent dependent. The structure of NaTeF has been determined by single crystal X-ray diffra~tion"~ and found to contain $-octahedral TeF; anions. The existence of several new polymorphs of KTeF and RbTeF have been identified and their structural proper- ties examined.'86 The compounds Fe(TPP)(OTeF,) and Fe(OEP)(OTeF,) together with their "0 analogues have been prepared and characterized by magnetic suscepti- bility measurements 'H and 19F NMR UV-vis and infrared spectroscopy and cyclic v~ltammetry.'~~ The results showed the complexes to contain high spin iron(1ri) and the relative ligand field strength of the OTeF anion to follow the order C1-> OTeF,-> ClO,.The crystal structure of Fe(TPA)(OTeF,)(THF) was described. A new compound of composition Tb2Te4O1 ,has been synthesized by the solid state reaction of TeOz and Tb,O at 700-800 "C in air.'** The material changed on prolonged treatment at 800 "C to isostructural Tb2Te4-p011-zy (y < 0.25) and under- went reaction with yttrium to form solutions of the type (Y1-xTbx)2Te4011 (0.01 < x < 1.0).The preparation and properties of the compounds AgTiZrTe and Ag2TiZrTe4 have been rep~rted"~ and shown to adopt similar structures to that of TiZrTe with 179 P. Plambeck-Fischer W. Abriel and W. Urland J. Solid State Chem. 1989 78 164. 1an A. M. Kini B. D. Gates M. A. Beno and J. M. Williams J. Chem. Soc. Chem. Commun. 1989 169. I81 A. Amarilla M. L. Veiga C. Pico M. Gaitan and A. Jerez Inorg. Chem. 1989 28 1701. 182 R. Ollitrault-Fichet H. W. Shu J. Rivet and J. Flahaut Mat. Res. Bull. 1989 24 351. 183 G. Brun J. F. Dumas A. Bruno and J. C. Tedenac J. Solid Stare Cfiem.,1989 81 129.184 A. M. Bonds D. Dakternieks R. Di Giacomo and A. F. Hollenkamp Inorg. Chem. 1989 28 1510. 185 A. du Bois and W. Abriel Mat. Res. Bull. 1989 24 633. 186 J.-P. Bastide P. Germain J.-M. Lttofft R. El Mail and N. Ba Chauh Mat. Res. Bull. 1989 24 293. 1x7 P. J. Kellett M. J. Pawlik L. F. Taylor R. G. Thompson M. A. Levstik 0. P. Anderson and S. H. Straws Inorg. Chem. 1989 28 440. 188 T. Endo A. Shibuya T. Sato and M. Shimada J. Solid State Chem. 1989 78 237. 189 Z. Cybulski and A. Feltz Z. Anorg. Allg. Chem. 1989 569 145. 48 E J. Berry an ordered array of titanium and zirconium atoms at the octahedral sites of the Cd12 type lattice and with Ag+ ions in the interlayer regions. The titanium(1v)-zirconium( ~v) telluride TiZrTe has attracted other attention in connection with potential battery application^'^^ in a study which confirmed an ordered structure and showed the material to have a lower ability for the intercalation of lithium than TiTe and ZrTe .The heat capacities and derived thermophysical properties of isostructural ZrTe and Hffe have been reported."' The compounds Li2TiTe06 and Li2SnTe0 have been s-nthesized and described in terms of the LiSb03 structure with Ti-Te ordering.'92 The oxides A(Tio.,Tel.,)06(A= K Rb Cs Ti) have been obtained as polycrystalline powders and shown to adopt defect cubic pyrochlore-type structure^.'^^ The new layered ternary chalcogenides of composition Ta3Pd3Te14 and TaNiTe have been prepared by high temperature reactions of the elements and shown by single crystal X-ray diffraction techniques to adopt layer structure^.'^^ Electrical conductivity measurements showed both compounds to be metallic.New routes for the synthesis of the compounds OS~(CO)~(~~-T~)~ and Ru3(C0)J p3-Te)2 have been des~ribed'~~ together with details of the synthesis and characterization of the new trimetallic cluster Fe20s3(CO),,( p4-Te)(p3-Te). Silver tellurite Ag2Te03 has been prepared from an aqueous solution and also by oxidation of Ag2Te in air.'96 Cadmium telluride thin films have been grown with a zinc blend structure on glass and tin oxide coated glass and with a wurtzite structure on psi and mica.19' The salts [(p-TePh) (HgPR~)3(Hg)](C104)2 (R = Ph 4-C,H4Me 4-C6H4C1) have been prepared19' and characterized by 3' P 12,Te and 199 Hg NMR spectroscopy.The compounds were shown to be of adomantanoid structure with novel tellurolate bridging. A new uranium tritelluride P-UTe, has been ~ynthesized'~~ and shown to crystallize with the NdTe3-type structure. 190 Z. Cybulski A. Feltz and M. Andratschte Mat. Rex Bull. 1989 24 157. 191 R. Shaviv E. F. Westrum H. Fjellvag and A. Kjekshus J. Solid State Chem. 1989 81 103. 192 J. Choisnet A. Rulmont and P. Tarte J. Solid State Chem. 1989 82 272. 193 A. Castro I. Rasines and X. M. Turrillas J. Solid State Chem. 1989 80 227. 194 E. W. Liimatta and J. A. Ibers J. Solid State Chem. 1989 78 7. 195 P. Mathur I. J. Mavunkal and V. Rugmini Inorg. Chem. 1989 28 3616. 196 S.R. Bharadwaj and G. Chattopadhyay J. Solid State Chem. 1989 80 256. 197 G. K. Padam and G. L. Malhotra Mat. Res. Bull. 1989 24 595. 198 P. A. W. Dean V. Manivannan and J. J. Vittal Inorg. Chem. 1989 28 2360. 199 H. Noel and J. C. Levet J. Solid State Chem. 1989 79,28.

ISSN:0260-1818    

DOI:10.1039/IC9898600021

出版商:RSC    

年代:1989

数据来源: RSC

摘要:

4 F CI Br I and Noble Gases By M. J. K. THOMAS School of Chemistry Thames Polytechnic London SEl8 6PF 1 Introduction This chapter follows the same format as last year in reviewing developments in the chemistry of the halogens and noble gases that have appeared in the literature over the past year. Following the precedent set last year only those papers that are unlikely to have been reviewed in other chapters of the Report have been included. The IXth European Symposium on Fluorine Chemistry took place in Leicester (UK) in early September last year. Plenary lectures were presented in the inorganic chemistry field on fluorine chemistry in its second century; the synthesis of new energetic materials and forty years of metal fluorides. The abstracts of all plenary invited and short lectures and all posters can be found in reference 1.2 Interhalogens and Related Ions Codeposition of Ar/F2 and Ar/PH3 at 16 K gives PH3F2 PHF, and the new molecule PH2F.2 In contrast the corresponding reaction between NH3 and F2 gave only NH3. .FZ which required photolysis to give NH,F. -.HF. The reaction between phosphine and fluorine apparently proceeds through a pentavalent activated complex. Self consistent field calculations have been performed on FNO (x = 1 2 3) and the geometries predi~ted.~ The predicted relative stabilities for the FNO i somers is FN0 > cis-FONO > trans-FONO. There is only a slight preference for a planar configuration for FONO,. Molecular chlorine can be made to disproportionate to C1F and C1- in several ways in HF for example when AgF is present in the reaction forming insoluble AgCl and ClF.4 When in an excess C1F5 ClF3 and C1F all undergo facile fluorine- oxygen exchange reactions with the nitrate anion forming FC102 unstable FClO and C10N02 respectively as the primary prod~cts.~ Whereas FC103 does not react ' J.Fluorine Chem. 1987 45. L. Andrews and R. Withnall Inorg. Chem. 1989 28 494. V. Moms G. A. Walker P. Jones Y. Cao S. C. Bhatia and J. H.Hall J. Phys. Chem. 1989 93 7071. M. Gambardella S. Kongpricha J. J. Pitts and A. W. Jache Can. J. Chem. 1989,67 1828. K. 0.Christe W. W. Wilson and R. D. Wilson Inorg. Chem. 1989 28 675. 49 M. J. K. Thomas with LiN03 at temperatures as high as 75 "C FC10 readily reacts with LiN03 or N20 to give C10N02 and O2 in high yield probably via formation of an unstable 02C10N02 intermediate.With excess CIF ClONO undergoes slow reaction to give FNO and C1,O as primary products. Magnetic susceptibility measurements to 4.2 K have been reported for O;[AsF,]- BrT[ Sb3Fl 1]- and I;[ Sb2Fl 1]-.6 The data have been interpreted using previous results from photoelectron spectroscopy and the known crystal structures. The Curie-Weiss law is obeyed by Br;[Sb3Fl,]- and Il[Sb2Fll]- shows relatively strong antiferromagnetic coupling. Tetramethyl ammonium salts of ClF, BrF, and BrF have been synthesized by metathetical reactions between tetramethylammonium fluoride and the correspond- ing caesium polyfluorohalate salts in dry acetonitrile.' They are white crystalline solids that are stable at room temperature.Two groups have independently reported on the structure of the BrF i~n.~.~ Both groups agree that the ion is almost perfectly octahedral in solid complexes despite having a pair of non-bonding electrons. In solution however the ion is fluxional on the NMR timescale. The IF ion in solution is distorted on the vibrational timescale and again fluxional by NMR.8 The differences between these two structures can be explained by considering the size of the Br atom with a maximum coordination of six towards fluorine being unable to accommodate a seventh ligand. Attempts to prepare CsIF result in the formation of Cs13F,, which is made up of three square pyramidal IF5 molecules joined by a bridging fluoride ion.' The latter does not occupy the sixth coordination site in the iodine octahedron but is displaced to the side -indirect evidence for the steric effect of the non-bonding electron pair in IF,.Spectrophotometric studies of the reaction of I with Et,todit (1) in ratios from 1 1 to 1 :2 in chloroform showed formation of a 1 :1 charge-transfer complex." In the solid state a 1:2 donor-acceptor complex was isolated. The two sulphur thioamide atoms of the ligand act as donors with respect to two I2 molecules. ,s-s \ S S Sodium fluoride and the Lewis acids NbF, TaF, and SbF5 have been used to fix precisely the levels of basicity and acidity in anhydrous HF in order to establish the acidity thresholds above which the cations If 1; ,and 1; can be generated in solution." Addition of an excess of F- causes disproportionation of each of the ' M.S. R. Cader R. C. Thompson and F. Aubke Can. J. Chem. 1989 67 1942. ' W. W. Wilson and K. 0.Christe Inorg. Chem. 1989 28 4172. * K. 0. Christe and W. W. Wilson Inorg. Chem. 1989 28 3275. A. R. Mahjoub A. Hoser J. Fuchs and K. Seppelt Angew. Chem. Int. Ed. Engl. 1989 28 1526. lo D. Atzei 0. Deplano E. F. Trogu F. Bigoli M. A. Pellinghelli A. Sabatini and A. Vacca Can. J. Chem. 1989 67 1416. 'I J. Besida and T. A. O'Donnell Inorg. Chem. 1989 28 1669. F Cl Br I and Noble Gases 51 cations to I2 and IF5. When these products are dissolved in HF and the acidity level adjusted appropriately the individual cations can be generated.The level of acidity is the principal determinant of the nature of the iodine cations generated in HF. Solid state 31P NMR spectroscopy has shown that Ph3PICI and Ph3PIBr prepared from Ph3P and IC1 or IBr in non-polar solvents have ionic structures Ph3PI+X-.12 New iodoammonium salts 0-C6H4( NH2)21+I- and 0-C6H4( NH2)21+ AsF have been prepared from o-phenylene diamine and I or If AsF .13 The former compound reacts with AlI to give the corresponding tetraiodoaluminate complex. Direct evidence was found for the N-I bond in the Raman spectra of the complexes [ v(N1) = 599-600 cm-'I. The room temperature 'H NMR spectra of the iodide and tetraiodoaluminate compounds show two resonances one due to C-H and the other to N-H protons but the spectrum of the hexafluoroarsenate salt shows only one resonance in the aromatic C-H region.This difference was explained as being due to intermolecular N- H proton exchange. At low temperatures resonances due to both N-H and aromatic protons appear. The equivalence of the N-H protons in all three complexes was explained by an equilibrium of cations (equation 1) and rapid exchange reactions. aNH2 NH21+ Very large first order rate constants have been measured for the rate of loss of ICl in basic and neutral solution^.'^ The rate varies inversely with chloride ion concentration since ICl(aq) is the reactive form. Hydrolysis of ICl(aq) to give HOI and C1- is extremely rapid. The new compounds Na[I(CN),].2H20 and K[I(CN),] have been prepared by the addition of I2 to concentrated aqueous solutions of sodium or potassium cyanide^.'^ The structures are made up of layer-like packages of cations water molecules and tri-halide-analogous anions I(CN):.The anion is strictly linear at the iodine atom and nearly linear at the carbon atoms. With BX3 (X = C1 Br I OCOCF3) CF31F2 undergoes fluorine exchange reac- tions to form CF31X2.16 The reactions of CF31F2 with (CF3),BNMe2 Me3SiNC0 and Me,SiNMeCOCF give the corresponding new trifluoromethyliodine( 111)-nitrogen compounds. The reaction of CF31F2 and Me,SiCl also gives CF31C12. It reacts with AgX (X = OCOCF, SCF3) to give the corresponding CF31X2 com- pounds and with Ph4AsC1 the novel ion [CF31C13]- was detected. Mossbauer parameters have been reported for a series of mono- and diaryl- iodine(111) carboxylates and for a series of tris(carboxylato)iodine(111) complexes (Table l).17,18 The Mossbauer data for both sets of complexes were shown to be '' K.B. Dillon and J. Lincoln Polyhedron 1989 8 1445. l3 I. Tornieporth-Oetting and Th. M. Klapoetke Polyhedron 1989 8 2911. 14 Y. L. Wang J. C. Nagy and D. W. Margerurn J. Am. Chern. Soc. 1989 111 7838. l5 K.-F. Tebbe and N. Krauss 2. Narurforsch. Teil B 1989 44 637; K.-F. Tebbe and N. Krauss Z. Naturforsch. Ted B,1989 44 149. 16 W. Tyrra and D. Naurnann J. Fluorine Chem. 1989 45 401. " M. Bardan T. Birchall C. S. Frarnpton and P. Kapoor Can. J. Chern. 1989 67 1878. l8 T. Birchall C. S. Frarnpton and P. Kapoor Inorg. Chern. 1989 28 636. M. J. K. Thomas Table 1 1271 Mossbauer parameters for a series of iodine( 111) carboxylates Compound s* mm s-l e2qQ/hMHz PhI( O,CCF,) -0.88 2708 PhI( 02CCH2CI) -0.93 2583 PhI(O,CCHCI,) -1.09 2698 (CfjF5)I(O2CCF3)2 -1.15 295 1 [PhI(O2CCF3)]20 -0.78 2572 Ph2102CCF3 -0.62 203 1 -1.83 3419 -1.60 3540 -1.75 3501 -1.75 3549 -1.74 3680 * Relative to KI.strongly dependent only on the primary bonding arrangement about the iodine and secondary bonding interactions have little or no effect. For the mono- and diaryl- iodine(111) complexes the isomer shift and quadrupole coupling constants show the expected trends with the electronegativity of the carboxylate group. The crystal structure of (C6F5)I(02CCF3)2 shows a distorted T-shaped AX3E2 arrangement around the iodine.The structure of I(02CMe) shows primary bonds to the three acetate groups and two strong intramolecular secondary bonds to two of the acetate groups forming an AX3Y2E2pentagonal-planar arrangement (2). The positive coup- ling constants are consistent with the central iodine nucleus being bound to three carboxylate groups in the xy plane with two non-bonding pairs of electrons axially disposed along the internuclear z axis. When reacted with MNO (M = alkali metal) IF5 readily exchanges two fluorine ligands for a doubly bonded oxygen.” In all cases MIF40 (M = Li K Cs) and FN02 are formed. The FN02 undergoes a fast secondary reaction with MN03 to give equimolar amounts of N205 and MF. The MF depending on M does or does K. 0. Christe W. W. Wilson and R.D. Wilson Inorg. Chern. 1989 28,904. F Cl Br I and Noble Gases 53 not undergo complexation with excess IF5. Pure MIF40 salts were prepared from MF 1,05 and IF5 in either MeCN or IF5 as solvent. A stable adduct is not formed between FN02 and IF at temperatures as low as -78”C contrary to a previous report. Excess IF7 reacts with MNO (M = Li Na) to give MF FN02 IF5 and half mole of 02,but no IFSO. With CsNO the products are analogous except that CsF reacts with IF5 and the excess IF7 to give CsIF6.21F and CsIF8 respectively. 3 Noble Gases Ab-initio calculations at the MP4(SDTQ)/6-311G(2df 2pd))//MP2/6-31G(d p) level of theory predict that the best candidates to form stable argon salts appear to be ArF+AuF and ArF+SbF .” High level ab-initio calculations predict that the HCNArF+ cation is a stable Ar-N bonded species with a binding energy of 160 kJ mol-’ comparable with the observed krypton analogue HCNKrF+.’* Non-relativistic quantum chemical ab-initio calculations including electron corre- lation effects have been carried out for the electronic ground state of the HCNKrF+ ion the first experimentally observed stable compound with a N-Kr bond.22723 The geometrical structure stability towards dissociation and the harmonic vibrational spectrum have been computed and agree with the experimentally determined values.The calculations suggest a stronger Kr-F bond than in KrF,. The recent synthesis of FKr-NCH+ together with its Xe analogue has made possible a comparison of the experimental properties of the bonds formed by nitrogen and fluorine to the noble gas atoms (Ng) Kr and Xe.24 The exceptional ability of the NgF+ ions to act as Lewis acids is related to the presence of holes in the valence shell charge concentrations of the Kr and Xe atoms that expose their cores.The mechanism of formation of the Ng-N bonds in the adducts of NgF+ with HCN is similar to the formation of a hydrogen bond. The energies of formation of these adducts are dominated by the large stabilization of the Ng atoms that result from increases in the concentration of the charge in their inner quantum shells. The first example of a species containing a Kr-0 bond Kr(OTeF5)2 has been prepared from KrF2 and B(OTeF,) at -90 to -1 12 “C in S0,ClF.” There was no direct evidence for FKrOTeF with excess KrF2 in contrast to XeF,.Liquid xenon has been used as an inert solvent for C-H oxidative addition reactions.26 There are no significant fluorine bridges in the structure of [MeCN-XeC6F5]+[(C6F,),BF2]-(Figure l) prepared at low temperature from XeF and B(C6F5) in non-conducting solvent^.^' Pentafluorophenylxenon( 11) fluoroborates have been prepared from XeF and B(C6F5)3 .28 They were character- ized by reaction with Te(C,F,) and C6FJ to give the novel cations [(C6F5),Te]+ and [(C,F,),I]+ respectively. 20 G. Frenking W. Koch C. A. Deakyne J. F. Liebman and N. Bartlett J. Am. Chem. SOC.,1989,111 31. 21 M. W. Wong and L. Radom J. Chem. SOC.,Chem. Commun. 1989 719. 22 W. Koch J. Chem. SOC.,Chem. Cornmun. 1989 215.23 I. H. Hillier and M. A. Vincent J. Chem. SOC.,Chem. Commun. 1989 30. 24 P. J. MacDougall G. J. Schrobilgen and R. F. W. Bader fnorg. Chem. 1989 28 763. 2s J. C. P. Sanders and G. J. Schrobilgen J. Chem. SOC.,Chem. Commun. 1989 1576. 26 M. B. Sponsler B. H. Weiller P. 0. Stoutland and R. G. Bergman J. Am. Chem. SOC.,1989 111 6841. 27 H. J. Frohn S. Jakobs and G. Henkel Angew Chem. fnt. Edn. EngL 1989 28 1506. 28 D. Naumann and W. Tyrra J. Chem. Soc. Chem. Commun. 1989 47; H. J. Frohn and S. Jakobs J. Chem. SOC.,Chem. Commun. 1989 625. M. J. K. Thomas FF F' 'F Figure 1 Bond lengths (A) and bond angle in [MeCNXeC,F,]+ The electronic structures of the known [Xe2F3]+ and unknown XeIF have been calculated by using ab-initio molecular orbital theory with polarized split-valance basis sets.29 Geometries were gradient optimized and force fields calculated.Both species are linear. The calculated and experimental structures for [Xe2F3]+ differ in that the experimental structure is bent at the central fluorine F, and Xe-F bond distances are calculated to be 0.09 A too long. The calculated vibrational frequencies are in reasonable agreement with the experimental values after scaling. The geometry and frequencies for XeIF show that the molecule consists of interact- ing IF and XeF fragments. The a bonding in [Xe2F3]+ is a good example of a hypervalent five centre six electron (5c 6e) bond. For XeIF the bonding is not as delocalized although the components of the 5c 6e hypervalent bond are still present.Displacement of BrF from BrF3AuF with XeF gives XeF5AuF .30 This salt reacts quantitatively with KrF in anhydrous HF below 273 K to give XeF,AuF,. The former salt is isostructural with XeF5AgF4 the structure of which contains double layers of XeF (Figure 2) and layers of AgF ,with all layers parallel to the Figure 2 Bond lengths (A) and bond angles in XeF ab plane. Differences between the structures of XeF,AgF and XeF,AuF have been attributed to the lower ligand charges in the anion of the former relative to the latter and these are in turn related to observed differences in the basicity and oxidizability of the anions. The first known compound having two Xe,Ft cations (Xe2F1,)~NiF~-has been prepared from NiF, KrF2 and XeF in anhydrous HF.3' The Xe2F:l ion consists of two XeF groups bridged by an additional common fluorine atom (Figure 3).29 D. A. Dixon A. J. Arduengo and W. B. Farnham Inorg. Chem. 1989 28 4589. 30 K. Lutar A. Jesih I. Leban B. Zemva and N. Bartlett Inorg. Chem. 1989 28 3467. 31 A. Jesih K. Lutar I. Leban and B. Zemva Inorg. Chem. 1989 28 2911. F C2 Br I and Noble Gases Figure 3 The structure of (Xe,F,,)+,NiFz-4 Hydrogen Halides The melting diagram of the D20-DF system has been determined.32 It is largely similar to the H20-HF system except that an additional phase 2D20-3DF which is stable between -78 and -71 "C is observed. The structure of this additional phase is strongly related to that of NH3-4HF. It appears to be a molecular adduct rather than an oxonium salt.The remaining intermediary phases viz D,O.DF D20-2DF and D20.4DF are isotypic with their protium counterparts. State-of-the-art ab-initio quantum mechanical methods including SCF second order Mldller-Plesset perturbation theory singles and doubles configuration interac- tion theory and the singles and doubles coupled cluster approach have been used to study HF H20 and CN- and their hydrogen-bonded complexes.33 The FH.-.CN- and FH- -.NC- complexes are isoenergetic with binding energies of 98 kJ mol-* in good agreement with experimental values. The N. .H hydrogen-bond is shorter than the analogous C. .H hydrogen-bond. The infrared spectra of the two complexes are also similar. The molecular complexes [OC-.HF( DF)] and [CO.-.HF(DF)] can be selectively formed in high yields by ultraviolet photofragmentation of matrix-isolated formyl The latter complex is the less stable form and is produced at much lower concentrations than the former. Hydrogen-bonded complexes of amides and HF have been prepared in solid Ar.35 The spectra of the complexes show that the HF is hydrogen-bonded to the carbonyl oxygen in the primary intermolecular interaction which is complemented by a 32 W. Poll M. Lohmeyer and D. Mootz Z. Naturforsch. Teil B. 1989 44 1359. 33 T. J. Lee J. Am. Chem. Soc. 1989 111 7362. 34 G. Schatte H. Willner D. Hoge E. Knoezinger and 0. Schrems J. Phys. Chem. 1989 93 6025. 35 R. B. Bohn and L. Andrews J. Phys. Chem. 1989 93 5684. M. J.K. Thomas secondary amido H-F interaction giving a cyclic structure (3). The amide-HF interaction increases with methyl substitution. Complexes of HF with disilane and four methylsilanes have been prepared and studied in an Ar matrix.36 The infrared spectrum of the disilane-HF complex is very similar to the silane-HF complex reported previously while the methyl- dimethyl- and trimethylsilane complexes with HF differ substantially from Si2H6. ..HF but were similar to each other. The HF stretching frequency decreases as the degree of methylation increases except for trimethylsilane which gave the highest HF stretch- ing frequency. The main interaction in the Si,H6...HF complex is between the acid hydrogen and the silyl hydrogen atoms while in the methyl- dimethyl and trimethyl- silane complexes cyclic structures are formed in which the fluorine atom interacts with a methyl hydrogen and the acid hydrogen interacts with a silyl hydrogen atom.The melting point diagram for the pyridine-HC1 system has been determined and reveals the existence of intermediary solid complexes py.xHC1 (x = 0.5 1 2 4 and 6).37 The structures of the x = 1 2,4 and 6 complexes have been determined. Pyridinium cations chloride anions and with the exception of the monoadduct HC1 molecules are hydrogen-bonded into various discrete molecular and complex- ionic structural units e.g. (4) and (5). Among these are the first poly(hydrogen chloride) anions H,C1,+l or [Cl(HCl),]-with n > 1 characterized by crystal structure analysis. c1 \ H \ H\ c1 Weak 1 1 hydrogen-bonded complexes of molecular H2 02,and N2 with HCl have been prepared in solid Ne at 4-5 K.38The H2 and N2 complexes are believed to be structurally similar to the corresponding HF complexes.The 0,-HC1 complex may be anti-hydrogen bonded. The 1:2 base/HCl complexes were also prepared as well as a 2 1 02/HC1 complex. 36 S. R. Davis and L. Andrews J. Phys. Chem. 1989 93 1273. 37 D. Mootz and J. Hocken Z. Nuturforsch. Teil B 1989 44 1239. 38 R. B. Bohn R. D. Hunt and L. Andrews J. Phys. Chem. 1989 93 3979. F Cl Br I and Noble Gases 57 5 0x0 Compounds The infrared spectra of HOF trapped in different solid matrices at low temperatures show that the vibrational frequencies are perturbed to extents that vary with basicity of the adjacent molecules.39 Exposure of HOF isolated in an Ar matrix to UV radiation results in photodissociation and the formation of two products thought to be O.-.[HFI2 and 02-..[HF] 2.The reaction of C1206 with excess GeCl at room temperature gives a liquid which after fractional distillation gives GeCl3C1O4 and GeC12(C104)2 .40 If an excess of C1206is used with GeCl the product is (C102)2Ge(C104)6. The compounds have mainly unidentate perchlorato groups strongly bonded to the germanium which is tetrahedrally coordinated in GeC13C104 but octahedrally coordinated in the other complexes. The structure of (C102)2Ge(C104)6 is analogous to that of the correspond- ing tin compound. The crystal structure of NaBrO2.3H20 has been determinated and shows Br-0 bond lengths of 170.2 and 173.1 pm.41 Bromine K-edge EXAFS measurements for NaBr02.3H20 and aqueous solutions of BrO give average Br-0 distances of 175 and 172 pm in solution.Comparison of the results obtained from the X-ray analysis and from EXAFS suggests that EXAFS results for related compounds of uncertain structure can be viewed with confidence. Evidence has been found for the existence of the iodyl ion IO; in sulphuric acid solutions of enhanced Complex dynamical behaviour has been found in the oxidation of SCN- with 10 in acidic media.43 When the thiocyanate is in excess the stoichiometry of the reaction is given by equation 2 and if the 10 is in excess the reaction is that shown in equation 3.10 + SCN-+ H,O -* SO:-+ CN-+ I-+ 2H+ (2) 710; + SSCN-+ 2H+ -+ I + 5ICN + 5SO;-+ H,O (3) In high acid concentrations the reaction initially produces 12 which is later con- sumed. 6 Structural Chemistry of the Main Group Halides The 35Cl and 37Cl solid state NMR chemical shifts of a series of chloride salts with cubic structures are highly correlated with the interionic separation and the elec- tronegativity of the cation.44 7 Halides and Oxohalides of the d-and f-Block Elements A wide range of d-and f-block transition metal oxides react with COBr to form either the metal bromide or the metal oxide bromide.45 The reaction is driven by 39 E. A. Appelman A. J. Downs and G. J. Gardner J. Phys. Chem. 1989 93 598. 40 M. Fourati M. Chaabouni J.L. Pascal and J. Potier Can. J. Chem. 1989 67 1693. 41 W. Levason J. S. Ogden M. D. Spicer M. Webster and N. A. Young J. Am. Chem. SOC.,1989,111,6210. 42 J. A. Leinsten Can. J. Chem. 1989 67 1892. 43 R. H. Simoyi I. R. Epstein and K. Kustin J. Phys. Chem. 1989 93 1689. 44 T. L. Weeding and W. S. Veeman J. Chem. SOC.,Chem. Commun. 1989 946. 45 M.J. Parkington K. R.Seddon and T. A. Ryan J. Chem. Soc. Chem. Commun. 1989 1823. 58 M. J. K. Thomas the elimination of C02. In this way VOBr, Mo02Br2 ReOBr, SmBr, and UOBr were prepared from V205 MOO, Re207 Sm203 and UO respectively. The crystal structure of Zn(en),F2-2H20 shows that it contains the first example of a di-anion cluster [F2(H20)2]2- in which two fluoride ions and two water molecules form a diamond-shaped array with strong hydrogen-bonds (Figure 4).46 The crystal structure of [(bipy),FNi -F- NiF(bipy),]+[ F( EtOH),( H20)2 J-.H20 reveals three different and rare fluorine environments (Figure 5).47 Figure 4 Bond distances (A) in [F2(HzO)z]2-EtOH I 4 ---F---HoH-'-."3-3F---HOH---F---HOH 2.697 2.709 I I 1 2.005 I 2.579 1.985 [(bipy),Ni] -F-[Ni(bipy),] EI t OH + t,70,XO Figure 5 Bond lengths (A) and bond angle in [(bipy),FNi-F-NiF(bipy)J+[ F(EtOH),( H202)2]-8 Graphite Fluorides and Intercalates The preparation and characterization of the various graphite fluoride phases have been discussed by Watanabe Nakajima and Touhara in a new book published in this review year.48 The chemical fluorination of second and third stage graphite fluoroarsenate salts with F2 in liquid HF at ambient temperatures produces a planar-sheet graphite fluoride with a C/F ratio as low as 1.3.49 Graphite salts Cl' MF, (MF = BF, AsF, PF,) can be used as anion-exchange resins for the preparation of the corresponding NF; salts." The graphite salts are highly resistant towards acids and oxidizing agents.Graphite intercalation compounds (GICs) of the acceptor type are formed with CIF only at temperatures near 0 0C.51Different compounds are obtained with and without HF. Thermal decomposition near room temperature or preparation at 20-50 "C lead to covalent graphite compounds which differ from graphite fluorides prepared at high temperatures. GICs of HgC12 have been synthesized by four 46 J.Emsley M. Arif P. A. Bates and M. B. Hursthouse J. Chem. Soc. Chem. Cornmun. 1989 738. 47 J. Emsley M. Arif P. A. Bates and M. B. Hursthouse J. Chem. SOC. Dalton Trans. 1989 1273. 48 N. Watanabe T. Nakajima and H. Touhara 'Graphite Fluorides' Elsevier Amsterdam and New York 1988. 49 R. Hagiwara M. Lerner and N. Bartlett J. Chem. Soc. Chem. Commun. 1989 573. K. 0.Christe and R. D. Wilson Inorg. Chem. 1989 28 4175. R. Pentenrieder and H. P. Boehm Z. Naturforsch. Teil B 1989 44,755. F Cl Br I and Noble Gases methods vapour phase from melts of pure HgCl, from melts of HgC12 and MC1 (M = alkali metal) and from solutions in concentrated aqueous HCl.52 Other GICs have been prepared with HNO, HC104 HRe04 and CF3COOH.53 The reactions are fast with the first three intercalates and slow and superimposed by side reactions with trifluoroacetic acid.Attempts to intercalate ClCH,COOH were unsuccessful. Vapour-grown graphite fibres heat-treated to 3200 "C and intercalated with AsF have been In air rapid de-intercalation is followed by slower loss of intercalate. The products of the reaction of solid Fe-GIC with FeCl depends on the C Fe ratios in the starting material^.^^ At low initial iron concentrations the product is FeCl,-GIC and as the iron concentration increases the products are FeC1,-GIC FeC1,-GIC (x < 2) and Fe-GIC. Ternary graphite intercalated phases have been prepared with CoCl and AlC13.56 52 P. Behrens M. Alidoosti F. Schulz and W. Metz Z. Naturforsch.Teil B 1989 44 721. 53 P. Scharff Z. Naturforsch. Teil B 1989 44 772. 54 I. Ohana M. S. Dresselhaus and M. Endo Carbon 1989 27 417. 55 A. W. Morawski and K. Kalucki Carbon 1989 27 951. 56 P. Pernot and R. Vangelisti Z. Naturforsch. Teil B 1989 44 761.

ISSN:0260-1818    

DOI:10.1039/IC9898600049

出版商:RSC    

年代:1989

数据来源: RSC

摘要:

5 Zn Cd Hg By D. T. RICHENS Department ofChemistry The Purdie Building The University St. Andrews Fife KY16 9ST 1 Zinc Bioinorganic and Biological Zinc.-A review of 65 references concerning the structure and mechanisms of action of Zn peptidases has appeared,' as has a separate review of 70 references on Zn carboxypeptidase A.2 Inhibition of CPA activity by an excess Zn2+-induced conformational change has been de~cribed.~ A molecular mechanics study of Zn coordination and H-bonding-solvent interactions in Carbonic Anhydrase I has a~peared.~ Zinc interactions with histidine and carboxylate residues as a link with protein structure and function have been disc~ssed.~ 'H NMR studies of water dispersion with anions6 and Co" substitution' in Zn-Cu superoxide dismutase have been reported.The structures of Zn(SR) (R = S-2,3,5,6-Me4C6H and S-2,4,6-Pr';C,H,) complexes have been presented' as models for the Zn(cy~)~(his)~ centre in transcription factor I11 A and related nucleic acid binding proteins. Detailed studies of tetrahedral thiophenolato and selenophenolato complexes of Zn" and Cd" have also a~peared.~ Trigonal planar [Zn(SR),]- complexes with bulky R groups have been characterized as alternative models for Zn-cysteine interaction." A close model of the Zn(cys),(his) centre in the gene-32 protein has been structurally characterized." Zinc(11) complexes of peptides; gly-cis cis-gly and N-acetylpenicill- amine have been discussed.12 Complexes of Zn" and Cd" with allopurinol have been prepared.' The structure of bis( 1-1eucinato)Zn" has appeared.I4 The ascorbic acid photoreduction of Zinc( 11) chlorophylls to produce metal-free derivatives has been rep~rted.'~ A study of electron transfer kinetics with Zn" substituted cyto- chrome-c has appeared.16 The structures of two Fe-Zn complexes containing ' B.W. Matthews Acc. Chem. Res. 1988 21 333. * D. W. Christianson and W.N. Lipscornb Acc. Chem. Res. 1989 22 62. J. Hirose and Y. Kidani J. Coord. Chem. 1988 18 165. A. Vedani D. W. Huhta and S. P. Jacober J. Am. Chem. SOC.,1989 111 4075. D. W. Christianson and R. S. Alexander J. Am. Chem. SOC.,1989 111 6412. L. Banci I. Bertini C. Luchinat R. Monnanni and A. Scozzafava Znorg. Chem. 1988 27 107. ' L.-J. Ming L. Banci C. Luchinat I. Bertini and J.S. Valentine Znorg. Chem. 1988 27 728. * D. T. Corwin and S. A. Koch Znorg. Chem. 1988 27 493. N. Ueyarna T. Sugawara K. Sasaki A. Nakamura S. Y. Yarnashita Y. Wakatsuki H. Yamasaki and N. Yasuoka Znorg. Chem. 1988 27 741. 10 E. S. Gruff and S. A. Koch J. Am. Chem. SOC.,1989 111 8762. D. T. Convin E. S. Gruff and S. A. Koch Znorg. Chim. Acta 1988 151 5. 12 I. Sovago T. Kiss K. Varnagy and B. Decock-Le-Reverend Polyhedron 1988 7 1089. 13 G. Hanggi H. Schmalle and E. Dubler Znorg. Chem. 1988 27 3131. 14 C. A. Steren R. Calvo 0. E. Piro and B. E. Rivero Znorg. Chem. 1989 28 1933. Is D. J. Simpson and K. M. Smith J. Am. Chem. SOC.,1988 110 2854. I6 H. Elias M. H. Chou and J. R. Winkler J. Am. Chem. Soc. 1988 110 429. 61 62 D. T.Richens bridging carboxylato groups have been pre~ented'~ as models for the Fe-Zn centre18 in red kidney bean purple acid phosphatase (PAP). A study of the replacement of the Zn" in PAP by Cd" has allowed a route to the apoenzyme." Studies of photo- induced long range electron transfer in Zn-Ru modified myoglobins have been reported.20 Zinc has been found to be in a trigonal bipyramidal coordination site in the structure of Haloenolase2' refined at 1.9 A. The interaction of Zn" with insulin has been described.22 Binary and ternary Zn" complexes with uridine have been discussed.23 Zinc Macrocyclic Complexes.-The structures of Zn" and Cd" complexes with interlocking macrocyclic 'catanand' ligands based on substituted 1 lo-phenanthro- line have been presented.24 The structures of [Zn2([30]aneNl,)( NCS)](C104)3,25 [Zn2([24]aneN8)C12]C1(C104).H20,26 and [Zn([ 12]aneN3)Br]Br27 have been repor- ted as has that of [Zn([9]aneN3)I2+ containing a single pendant bipyridyl.28 Zinc( 11) has been found to be trigonal bipyramidally coordinated to the phenol pendant macrocycle 2-( 2-hydroxypheno1)- l,5,9-triazacyclododecane.29Studies on Zn" com- plexes of several sterically hindered tetraarylporphyrins have appeared3' as have photoredox reaction^,'^ C NMR,32 resonance Raman,33 intermolecular spin coup- charge transfer kinetics,35 and electrochemical studies36 on other Zn porphyrin complexes.Tetra-anionic Zn porphyrins have been studied in micellar aggregate^.^^ The photochemistry of exciton coupling in Zn" porphyrin dimers with naphthalene bridges has been studied38 as have light induced conformational switching and allosteric effects in several other Zn porphyrin dimer complexes.39 The structure of the novel rr-cation radical dimer complex; [Zn(OEP'.)(OH2)]2(C104)2has a~peared.~' 'Twisted' Zn" porphyrin dimer complexes have been investigated as l7 A.S. Borovik L. Que V. Papaefthymiou E. Munck L. F. Taylor and 0. P. Anderson J. Am. Chem. SOC.,1988 110 1986. A. S. Borovik V. Papaefthymiou L. F. Taylor 0. P. Anderson and L. Que J. Am. Chem. SOC.,1989 111 6183. 18 J. L. Beck J. DeJersey and B. Zerner J. Am. Chem. SOC.,1988 110 3317. 19 J. L. Beck M. J. McArthur J. DeJersey and B. Zerner Inorg. Chim. Acta 1988 153 39. 20 A. Axup M. Albin S. I. Mayo R.J. Crutchley and H. B. Gray J. Am. Chem. SOC.,1988 110 435. 21 L. Lebioda and B. Stec. J. Am. Chem. SOC.,1989 111 8511. 22 F. Gaizer Polyhedron 1989 8 2065. 23 B. Taqui-Khan R. Madhusudan Raju and S. M. Zakeeruddin J. Coord. Chem. 1988 16 237. 24 A. M. Albrecht-Gary C. Dietrich-Buchecker Z. Saad and J-P Sauvage J. Am. Chem. SOC.,1988 110 1467. 25 A. Bencini A. Bianchi E. Garcia-Espana S. Mangani M. Micheloni P. Orioli and P. Paoletti Inorg. Chern. 1988 27 1104. 26 A. Bencini A. Bianchi P. Dapporto E. Garcia-Espana M. Micheloni and P. Paoletti Inorg. Chem. 1989 28 1188. 27 P. M. Schaber J. C. Fettinger M. R. Churchill D. Nalewajek and K. Fries Inorg. Chem. 1988,27,1641. 28 N. W. Alcock F. McLaren P. Moore G. A. Pike and S. M. Roe J.Chem. SOC.,Chem. Cornmun. 1989 629. 29 E. Kimura T. Kioche and K. Toriumi Inorg. Chem. 1988 27 3687. 30 M. M. Williamson C. M. Prosser-McCartha S. Mukundan and C. L. Hill Inorg. Chem. 1988,27 1061. 31 J. Kalyanasundaram J. A. Shelnutt and M. Gratzel Inorg. Chem. 1988 27 2820. 32 R. Y. Saleh and D. K. Straub Inorg. Chim. Acta 1989 100 9. 33 V. A. Walters J. C. dePaula G. T. Babcock and G. E. Leroi J. Am. Chem. SOC.,1989 111 8300. 34 H. Song N. P. Roth C. A. Reed and W. R. Scheidt Inorg. Chem. 1989 28 1839. 35 A. M. Crouch D. K. Sharma and C. H. Langford J. Chem. SOC.,Chem. Commun. 1988 307. 36 K. M. Kadish C. Araullo G. B. Maiya D. Sazou J. M. Barbe and R. Guilard Inorg. Chem. 1989 28 2528. 37 K. M. Kadish G. B. Maiya C. Araullo and R.Guilard Inorg. Chem. 1989 28 2725. 38 A. Osuka and K. Maruyama J. Am. Chem. SOC. 1988 110 4455. 39 C. A. Hunter M. N. Meah and J. K. M. Sanders J. Chem. Soc. Chem. Commun. 1988,692. 40 H. Song C. A. Reed and W. R. Scheidt 1.Am. Chem. SOC.,1989 111 6867. Zn,Cd Hg 63 models for biological excitation en erg^.^' A tetranuclear Zn" complex is formed with the macrocyclic ligand generated via Schiff -base condensation of 2,6-bis( aminomethyl)4-methyl phenol and 2,6-diformyl-4-methylphen01?~ Zinc(11) com-plexes of two 1,4-piperazine based penta-aza macrocycles have been The structure of polymeric 5-pyridyl-l0,15,20-triphenyl porphyrinato Zn" has appeared.44 Photochemical studies on several water soluble Zn porphyrins have been described.45 Kinetic studies of Zn" incorporation into a polyvalent porphyrin; tetrakis(3,5-diBut-4-hydroxypheny1)porphyrin have been investigated.& The struc- tures of several Zn complexes with l,5-crown-5 and 18-crown-6 have appeared4' as has the structure of [Zn([9]aneS3)2](C104)2.2CH3CN.48 Several mixed donor macrocyclic complexes of Zn" and Cd" with pendant carboxylate groups have been reported.49 The electronic structure of Zn" phthalocyanine has been ~tudied.~' The FAB MS of dichloro(tet a)complexes of Zn" and Cd" have been discus~ed.~' Organometallic Zinc Chemistry.-The structures of Zn( q5-C5Me5)2 ,52 Zn( q5-CSMe4Ph),,52 Zn( C$5)2(t.h.f.)2 ,53 di-q,-flu~renylbis(t.h.f.)zinc,~~1,l-dichloro-2,2,2-trifluoroethylzinc chloride" and the mixed ligand cluster Zn4Ni2( q5-C5H5)4( q5-C5Me5)256 have appeared.The synthesis of 2-(dimethylaminomethyl)-5-ferrocenyl complexes of Zn" Cd" and Hg" have been rep~rted.~' Thermolytic bond strengths in a range of simple Zn alkyls have been inve~tigated.~~ Intramolecular interactions between Zn and the CrC bond in dihexyn-4-ylzinc have been studied.59 Organozinc derivatives of alkyl-cu -bromomethyl and ethyl acrylates have been characterized.60 The use of polar aprotic solvents to enhance the reactivity of certain Zn alkyls has been discussed.6' The structure of diethylzinc( 18-crown-6) has appeared.62 Ethyl-@,? and 6-zinc esters have been found to react with aldehydes in a remote Reformatski reaction to produce ethyl-y S and E-hydroxy esters.63 41 A.Osuka K. Maruyama I. Yamazaki and N. Tamai J. Chem. SOC.,Chem. Commun. 1988 1243. 42 M. Bell A. J. Edwards B. F. Hoskins E. H. Kachab and R. Robson J. Am. Chem. Soc. 1989,111,3603. 43 N. W. Alcock P. Moore C. J. Reader and S. M. Roe J. Chem. Soc. Dalton Trans. 1988 2959. 44 A. M. Schachter E. B. Fleischer and R. C. Hattiwanger J. Chem. SOC.,Chem. Commun. 1988 960. 45 (a) Y. Kinumi and I. Okura Inorg. Chim. Acta 1988 153 77; (b) E. Mikros A. Gaudemer and R. Pasternack ibid. 1988 153 199; (c) I. Okura Y. Kinumi and T. Nishisaka ibid. 1989 156 169. 46 T. Ozawa T. Takai and A. Hanaki ibid. 1989 159 225. 47 V. K. Bel'sky N. R. Streltsova B. M. Bulychev P. A. Storozhenko L. V. Ivankina and A. I. Gorbunov Znorg. Chim. Acfa 1989 164 211. 48 H.J. Kuppers K. Weighardt B. Nuber and J. Weiss 2. Anorg. Allg. Chem. 1989 577 155. 49 K. R. Adam J. Leong L. F. Lindoy P. Hendry S. V. Smith and D. Yellowlees J. Coord. Chem. 1988 19 189. E. Kanezaki J. Coord. Chem. 1988 18 113; N. El Khatib B. Boudjema M. Maitrot H. Chermette and L. Porte Can. J. Chem. 1988,66 2313. 51 C. L. Maclaurin J. M. Miller and M. F. Richardson Can. J. Chem. 1989 67 797. 52 B. Fischer P. Wijkens J. Boersma G. Van Koten W. J. J. Smeets A. L. Spek and P. H. M. Budzelaar J. Organomef. Chem. 1989 376 223. 53 M. Weidenbruch M. Herrndorf A. Schafer S. Pohl and E. Saak J. Organomet. Chem 1989 361 139. 54 B. Fischer J. Boersma G. Van Koten W. J. J. Smeets and A. L. Spek Organometallics 1989 8 667. 55 D. Bellus B. Klingert R.W. Lang and G. Rihs J. Organornet. Chem. 1988 339 17. 56 B. Fischer H. Kleijn J. Boersma G. Van Koten and A. L. Spek Organomefallics 1989 8 921. 57 C. Kruger K.-H. Thiele M. Dargetz and T. Bartik J. Organomet Chem. 1989 362 147. 58 1. E. Gumrukcuoglu J. Jeffrey M. F. Lappert J. B. Pedley and A. K. Rai J. Organomet. Chem. 1988 341 53. 59 K. B. Storowieyeski J. Organomet. Chem. 1988 347 1. 60 N. El Alami C. Belaud and J. Villieras J. Organomet. Chem. 1988 348,1; ibid. 1988 353 157. 61 J. Grondin M. Sebban P. Vottero H. Blancou and A. Commeyras J. Organomet. Chem. 1989,362,237. 62 A. D. Pajerski G. L. Berstresser M. Parvez and H. G. Richey J. Am. Chem. Soc. 1988 110 4844. 63 Y. Tamaru T. Nakamura M. Sakaguchi H. Ochiai and Z. Yoshida J.Chem. Soc. Chem. Commun. 1988 610. D. T. Richens Solid State and Electrochemical Studies.-A review of 53 references on the influence of complex formation and solvation on the electrode reactions of Zn2+ and Cd2+ in aprotic solvents has appeared.64 The electrochemical synthesis of Zn and Cd derivatives of a,o-alkanedithiols has been reported.65 Photoelectron spectroscopic studies of ZnO ZnCl, and [ZnCl4I2- has linked covalent bonding properties to the high thermodynamic stability of 3d" complexes.66 An organometallic route to micron size 'whiskers' of ZnS has been de~eloped.~~ A mild synthesis of ZnSe CdSe and CdTe via metal alkyls and silyl chalcogenides has been reported.68 The structural and magnetic properties of Zn(phen),(TCNQ-) have been described.69 Quenching of the superconduction in YBCO has been reported to occur via Zn" substitution of 10% of the Cu" sites.70 EXAFS and X-ray absorption edge studies of the ZnO-based methanol synthesis catalyst have appeared.71 The sonochemistry of Zn powder has been st~died.~' The structure of Zn-graphite has been disclosed by analytical electron micro~copy.~~ Zinc sulphate in natural sand has been found to be a remarkably specific catalyst for the oxidation of pyridine~.~~ The use of polynuclear Zn porphyrins having semi-rigid cavities to increase chromatographic mobility and ease of separation on silica has been de~cribed.~' The metallomesogenic complex; [Zn(ROC6H4CS2)2],(R = C4H9) (Figure 1) has been found to show liquid crystalline behaviour arising from its rod-like structure76 Figure 1 Structure of [{Zn(SZCC6H40C4H9)2}] (Reproduced by permission from Polyhedron 1988 7 1865).Coordination Chemistry.-Structural characterization of the linear trinuclear croton- ates; Mzn,(crot),(base) (M = Zn Cd Hg base = quinoline) has appeared.77 Ligand-ligand interactions in mixed malonate-2,2-bipyridine Zn" complexes have 64 S. Fronaeus Coord. Chem. Rev. 1988,88 203. 65 H. Mabrouk and D. G. Tuck Inorg. Chim. Acta 1988 145 237. 66 S. V. Didzuilis S. L. Cohen and K. D. Butcher Inorg. Chem. 1988 27 2238. 67 C. L. Czeka M. S. Rau G. L. Geoffroy T. A. Guiton and C. G. Pantano Inorg. Chem. 1988,27,3267. 68 S. M. Stuczynski J. L. Brennan and M. L. Steigerwald Znorg. Chem. 1989 28 4432.69 A. Bencini S. Midollini and C. Zanchini Inorg. Chem. 1989 28 1963. 70 R. Jones P. P. Edwards M. R. Harrison T. Thanyasini and E. Sinn J. Am. Chem. Soc. 1988,110,6716. 71 L-S. Kau K. 0. Hodgson and E. I. Solomon J. Am. Chem. SOC.,1989 111 7103. 72 K. S. Suslick and S. J. Dokkycz J. Am. Chem. Soc. 1989 111 2342. 73 A. Furstner H. Weidmann and F. Hofer J. Chem. Soc. Dalton Trans. 1988 2023. 74 R. D. Gillard and D. P. J. Hall J. Chem. SOC.,Chem. Commun. 1988 1163. 75 H. L. Anderson and J. K. M. Sanders J. Chem. SOC.,Chem. Commun. 1989 1714. 76 H. Adams N. A. Bailey D. W. Bruce R. Dhillon D. A. Dunmur S. E. Hunt E. Lalinda A. A. Maggs R. Orr P. Styring M. S. Wraggs and P. M. Maitlis Polyhedron 1988 7 1861. 77 W. Clegg 1.Little and B. P. Straughan Inorg. Chem. 1988 27 1916. Zn Cd Hg 65 been ~tudied.'~ A gas phase electron diffraction study of Zn(S2CNMe2)* monomers has appeared.79 Transmetallation reactions on polynuclear Cu" complexes with Zn Cd and Hg(NS)2 complexes (NS = S-methylisopropylidenehydrazinecarbodithio-late) have been reported.80 Variable pressure kinetic and equilibrium studies of 2-chloro- 1 ,lO-phenanthroline" and bipyridines2 complexes of Zn" and Cd" have appeared. A soluble ZnO-methanol synthesis catalyst model; [HZnOC(CH,),] has been reported.83 Dichlorobis(4-nitroso- N,N-dimethylaniline)zinc(11) has an unusual 0-bonded arylnitroso ligand.84 Studies on new organ~phosphate,~~ phosphite,86 and ph~sphonate~~ complexes of zinc have been reported.13C NMR studies in solution of Zn" complexes of dipropylenetriamine,88 N-(2-aminoethy1)propane- 1,3- diamine,88 4,7-diazadecane- 1 lO-diamine" and 4,8-diazaundecane-l 1 1 -diamine89 have appeared. The low frequency I.R. spectral and thermal behaviour of N,N',N"-trimethylethylenediamine complexes of Zn Cd and Hg has been studied." Flexibil- ity in the coordination behaviour of propane-1,3-diamine towards Zn" and Cd" in MX2L2 complexes (X = C1 Br I) has been detected." The structure of ZnC12L (L = the tridentate ligand; 2,6-bis( benzimidazol-2'-yl)pyridine)has been reported.92 An a-bromoesterimine condensation reaction promoted by Zn-trimethylchlorosilane has been characteri~ed.~~ The structure of Zn(S,CNBu",)( 1,lO-phen) has appeared.94 Tetrahedral Zn" complexes with diphenyl-2-pyridylmethane have been studied.95 ZnFe(CN),N0.3H20 was found to contain a Zn-NEC-Fe bridge.96 The binding of up to six Zn2+ ions at functionalized side chain positions of cyclophosphazenes has been reported.97 Zinc( 11) and Cd" complexes of 1,3-bis(2-pyridy1)-1,3-propanedione and its N,N'-dimethyl analogue have been reported.98 Thermody- namic studies on the formation of halo complexes of Zn" and Cd" in acetonitrile 78 P.Amico R. P. Bonoma R. Calo V. Cicinotta P. G. Daniele G. Ostocoli and E. Rizzarelli Znorg. Chem. 1989 28 3555. 79 K. Hagen C. J. Holwill and D. A. Rice Znorg. Chem. 1989 28 3239. 80 A. Abu-Ragabah G. Davies M. A. El-Sayed A. El-Toukhy and M. Henery Znorg. Chem. 1989,28,1156. " G. Laurenczy Y.Ducummon and A. E. Merbach Znorg. Chem. 1989 28 3024. 82 Y. Ducummon G. Laurenczy and A. E. Merbach Inorg. Chem. 1988 27 1148. 83 T. D. Neils and J. M. Burlitch Inorg. Chem. 1989 28 1607. 84 S. Hu D. M. Thompson P. 0.Ikewere R. J. Barton K. E. Johnson and B. E. Robertson Znorg. Chem. 1989 28,4552. 85 C. Y. Ortiz-Avila P. R. Rudolf and A. Clearfield Inorg. Chem. 1989 28 2137. M. M. Armstrong U. Kramer P. W. Linder R. G. Torrington and T. A. Modro J. Coord. Chem. 1989 20 81. 86 C. Y. Ortiz-Avila P. J. Squattrito M. Shieh and A. Clearfield Inorg. Chem. 1989 28 2608. 87 K. J. Martin P. J. Squattrito and A. Clearfield Znorg. Chim.Acta 1988 155 7. C. Y. Ortiz-Avila P. R. Rudolf and A. Clearfield J. Coord. Chem. 1989 20 109. 88 S. P. Dagnall D.N. Hague and A. D. Moreton J. Chem. SOC.,Dalton Trans. 1988 1989. 89 D. N. Hague and A. D. Moreton J. Chem. SOC.,Dalton Trans. 1989 1171. 90 N. Bell Inorg. Chim.Acta 1988 141 173. 91 G. Ciani M. Moret A. Sironi S. Bruni F. Cariato A. Pozzi T. Manfredini L. Menabue and G. C. Pellacani Inorg. Chim.Ada 1989 158 9. 92 S. B. Sanni H. J. Behm P. T. Buerskens G. A. vanAlbada J. Reedijk A. T. H. Lenstra A. W. Addison and M. Palaniandava 1. Chem. Soc. Dalton Trans. 1988 1429. 93 F. P. Cossio J. M. Odriozola M. Oiarbide and C. Paloma J. Chem. SOC.,Chem. Commun. 1989 74. 94 N. A. Bell E. Johnson L. A. March S. D. Marsden I. W. Nowell. and Y. Walker Inorg. Chim.Am 1989 156 205. 95 J. R. Allan B. Carron A D. Paton K. Turvey H. J. Bowley and D.L. Gerrard Znorg. Chim.Acta 1989 158 249. 96 D. F. Mullica E. L. Sappenfield D. B. Tippin and D. H. Leschnitzer Inorg. Chim.Acta 1989 164 99. 97 R. Bertani G. Facchin and M. Gleria Inorg. Chim. Acta 1989 165 73. 98 F. Teixidor R. Garica J. Pons and J. Casaba Polyhedron 1988 7 43. 66 D. T. Richens have appeared99 as have equilibration studies involving nitrite complexes of Zn" and Cd" (1:1 and 1:2) and Hg" (1:1 1:2 and 1:4).''' The Zn" complex of the Schiff-base derived from 3-amino-3-phosphonopropionicacid and 5'-deoxy-pyridoxal has been characterized."' Soluble Zn" and Cd" Schiff-base complexes formed from salicylaldehye-5-sulphonateand polyamines have been studiedlo2 as have those deriving from the Schiff-base condensation of 2,6-diacetylpyridine with S-methyldithio~arbazate,'~~ 2-(2-arnin0ethyl)pyridine,"~ hi~tamine,''~ and the amino acids phenylalanine tyrosine and hi~tidine."~ Schiff-base complexes of Zn" derived from 2-acetylpyrrole have been described.'05 13C NMR has been used to study complex formation of salicylaldehyde-derived Schiff-bases with ZnX (X = C1 I).'06 Studies on ethylhydrazine complexes of Zn" and Cd" have appeared.'07 Mixed-ligand complexes (1 :1) of Zn" with 3-hydroxynaphthoate and picolinate have been studied in H,O/dioxane mixtures.'08 The structures of molecular [M(Se4)J2- complexes (M = Zn Cd and Hg) have appeared.'" Complex forma- tion and acid dissociation behaviour in Zn" and Cd" complexes of 2,5-toluenediamine- N,N'-disuccinic acid have been reported.' 'O Complex formation of CN- with Zn" at high pH has been studied.At pH > 8.5 the predominant complex formed is [Zn(CN)3(OH)]2-.' '' Hydridozinc complexes are reported to be formed uia the reaction of ZnH' with molecules containing acidic hydrogen atoms."' The successful extraction of MC12 (M = Zn Cd Hg) into chloroform in the presence of a NaOH( NaC1)-n-alkyloligo( oxyethy1ene)carboxylic acid mixture has been rep~rted."~ A Raman spectral study of the ZnBr-DMSO system has ap~eared.''~ The structure of trans-diaquabis( 2-thiazolidine carboxylato)zinc(11) has been characterized.' l5 Trigonal bipyramidal Zn" coordination is present in the chain structure of [Zn2(C,H3(C02),)2]2-.' l6 2 Cadmium Bioinorganic and Biological Cadmium. -A review of 198 references concerning the use of '13Cd NMR spectroscopy in coordination compounds and Cd containing proteins has a~peared."~ The proceedings of the 3rd 1.U.P.A.C cadmium conference consisting of 18 articles have been published as part of a general review of cadmium 99 D.P. Graddon and C. S. Khoo Polyhedron 1988 7 2129. I00 F. Bedia Erim and E. Avsar Polyhedron 1988 7 213. 101 A. E. Martell and B. Szpoganicz Inorg. Chem. 1989 28 4199. I02 D. F. Evans and D. A. Jakubovic Polyhedron 1988 7 1881. 103 S. M. M. H. Majumder M. Abbar-Ali F. E. Smith and M. A. U. Mridha Polyhedron 1988 7 2183. 104 W. L. Kwik K. P. Ang and A. W. N. Tay Polyhedron 1988 7 695. 105 W. J. Birdsall J. Coord. Chem. 1988 17 291. 106 F. A. Bottino P.Finocchiaro and E. Libertini J. Coord. Chem. 1988 16 341. 107 A. A. Rahman M. P. Brown M. M. Harding C. E. Keggan and D. Nicholls Polyhedron 1988,7 1147. 108 E. Casassas R. Tauler and G. Fonrodona Polyhedron 1988 7 1335. 109 R. M. Herath Banda J. Cusick M. L. Scudder D. C. Craig and I. G. Dance Polyhedron 1989,8 1995. 110 J. Fuentes R. Reboso and A. Rodriguez Polyhedron 1989 8 1365. 111 F. Marsicano C. Monberg B. S. Martincigh K. Murray P. M. May and D. R. Williams J. Coord. Chem. 1988 16 321. 112 N. A. Bell and A. L. Kassyk J. Organomel. Chem. 1988 345 245. 113 J. Stnelbicki W. Charewitz J. Beger and L. Hinz Can. J. Chem.,1988,66,2640 and ibid. 1988,66 1695. 114 J. van Heuman T. Ozeki and D. E. Irish Can. J. Chem. 1989 67 2030. 115 M.Nagase Y. Yukawa Y. Inomata and T. Takeuchi Bull. Chem. SOC.Japan 1989 62 3247. I16 C. Robl Z. Anorg. AIIg. Chem. 1988 561 57. 117 M. F. Summers Coord. Chem. Rev. 1988 86 43. Zn Cd Hg 67 toxicology.'" A separate review of 'cadmium in the aquatic environment' has also appeared."' The synthesis and structures of CdC12L4 and CdL2.2H20 (L = the antitumour drug 6-mercaptopurine) have been reported.12' The effectiveness of Cd" in promoting sulphonamide nitrogen deprotonation has been investigated by 'I3Cd NMR polarographic and pH potentiometric studies on the Cd-N- tosylglycinate and Cd-N-dansylglycinate systems12' in both water and methanol/water. '13Cd NMR has been used to study Cd" interaction with several other N-protected amino acids together with a report'22 of the structure of Cd(t~syl-P-alaninate)~-tetrahydrate.'I3Cd NMR has also been used to study the 1:1 binding of Cd" to the 18-residue 'finger' peptide of the HIV-1 nucleic acid binding protein.'23 Complex formation of Cd" with the amino acids a~partate,'~~ ~erine,'~~ gl~tarnate,'~~ and iso~erine,'~~ and the peptide l-histidylglycine'26 has been investigated. An FTIR and Raman spectroscopic study of Cd binding to DNA has been re~0rted.l~~ The structure of C~(BU\NCS~)~ has been discussed in relation to Cd coordination chemistry in chelate therapy.'28 Cadmiurn(I1) complexes with 4,6-diamine-2-methylthio-5-nitro~opyrimidine,'~~ guanosine,130 and vitamin D313' have also been investigated. Cadmium is concluded to have pentagonal bipyramidal coordination site in parv- albumin arising from a 'I3Cd NMR study.'32 A '13Cd NMR study of cadmium substituted into hern~globin'~~ has also been reported.and my~globin'~~*'~~ Cadmium Macrocyclic Complexes.-CdX2L complexes (X = C1 Br I; L = the novel hexaaza ligand; 2,5,8,10,13,16-hexaazapentacyclo[8.6.1. 12.5.09*' 8.0'3~'7]octadecane have been studied.'35 Thermodynamic studies of the formation and dissociation of Cd" with polyazacycloalkanes; [3k]aneNk (k = 6-1 1)have appeared.'36 For values of k between 6-8 mononuclear complexes are formed whereas for k > 8 dinuclear complexes result. The structure of the dinuclear complex Na[ Cd2C12L]( C104)3 A (L = [30]aneNlo) was re~0rted.l~~ polymeric (Cd3L2) complex (L = 4,7,10-trioxa-l,13-dithia(2,5),1,3,4-thiadiazolophane)has been ~haracterized.'~~ I I8 M.Stoeppler and M. Piscator 'Cadmium-Environmental Toxin' Series 2 Springer-Verlag 1988 235pp. 119 J. 0. Nriagu and J. B. Sprague 'Cadmium in the Aquatic Environment' John Wiley 1987. 120 E. Dubler and E. Gyr Inorg. Chem. 1988 27 1466. 121 G. Battistuzzi-Gavioli M. Borsari G. C. Pellacini L. Menabue M. Sola and A. Bonamartini-Corradi Inorg. Chem. 1988 27 1587. 122 G. Battistuzzi-Gavioli L. Menabue M. Saladini M. Sola A. Bonamartini-Corradi and L. P. Battaglia J. Chem. SOC.,Dalton Trans. 1989 1345. 123 T. L. South B. Kim and M. F. Summers J. Am. Chem. SOC.,1989 111 7. 124 E. Bottari M. R. Festa and R. Jasionowska 1. Coord. Chem. 1988 20 209 and ibid 1988 17 245.125 G. Arena V. Cucinotta E. Rizzarelli P. G. Daniele G. Ostacoli and S. Sammartano J. Chem. SOC. Dalton Trans. 1988 1267. 126 P. G. Daniele 0.Zerbinati R. Arugg and G. Ostacoli J. Chem. SOC.,Dalton Trans. 1988 1115. 127 S. Alex and P. Dupuis Znorg. Chim. Acta 1989 157 271. 128 J. S. Casas A. Sanchez J. Brova S. Gracia-Fontan E. E. Castellano and M. M. Jones Znorg. Chim. Acta 1989 158 119. 129 M. A. Romero J. M. Salas R. Lopez and M. D. Gutierrez Polyhedron 1988 7 659. 130 S. T. Trisak and B. M. Rode Inorg. Chim. Acta 1989 160 249. 131 L. Qitao L. Yi and Z. Feng Polyhedron 1989 8 1953. 132 A. L. Swain and E. L. Amma Inorg. Chim. Acta 1989 163,5. 133 M. A. Kennedy and P. D. Ellis J. Am. Chem. SOC.,1989 111 3195. I34 J.A. Gowan and H. B. Gray Inorg. Chem. 1989 28 2074. 135 H. Strasdeit W. Saak Pohl W. L. Driessen and J. Reedijk Inorg. Chem. 1988 27 1557. 136 A. Bencini A. Bianchi M. Castella M. Di Vairi J. Faus E. Garcia-Espana M. Micheloni and P. Paoletti Znorg. Chem. 1989 28 347. 137 R. Bonomo F. Bottino F. R. Fronczek A. Mamo and S. Pappalardo Znorg. Chem. 1989 28,4592. 68 D. T. Richens Structural dislocation behaviour of Cd" and Zn" with some 02N3-donor macrocycles containing 17,18 and 19-membered rings has given rise to some metal ion binding spe~ificity.'~~ A report on further studies of Cd" and Zn" complexes with catanands has appeared.139 Studies on a 22 n-electron expanded porphyrin cadmium complex having pentagonal bipyramidal geometry have a~peared.'~' Axial coordination of 0-donor ligands to tetraphenylporphyrinatocadmium has been The struc- ture of the cyclic hexaphosphate complex Cd3P6Ol8-6H20 An has been re~0rted.l~~ insight into It3Cd NMR shielding principles has been gained following investigations on the cadmium complex with the macrocyclic ligand derived from the 2 :2 Schiff- base condensation of 2,6-diformylpyridine and 1,2-diaminoben~ene.'~~ Solid State Chemistry and Catalysis.-The synthesis of nanometer-size colloidal clusters of CdSe using organometallic precursors in inverse micellar solution has been reported.lU Clusters of CdSe have also been prepared via the pyrolysis of Cd(SePh),( Et2PCH2CH2PEt2).'45 Photoluminescent studies on CdSe in the presence of arnine~'~~ have been and on both CdSe and CdS in the presence of 01efins'~~ reported.An EXAFS and X-ray study of the stabilization of clusters of CdSe in Zeolite Y has appeared'48 as have similar studies with regard to the optical properties of CdS in a range of Zeolite hosts.'49 CdS mediated photoelectric effects on bilayer lipid membranes have been studied.I5' Photoreduction of C02 to give 2-carbon acids mediated by CdS has been rep~rted'~' as has the similarly mediated photore- duction of aromatic ketones to alcohols and/or pinac01s.'~~ The overgrowth of CdS on conducting polymers has been studied.ls3 Investigations into the mechanism of electrodeposition of CdSe from SeS0;- solutions have been de~cribed.'~~ Coordination and Organometallic Chemistry.-The structure of (Et4N)2[ M2C14( OC6H4CH3-p)2] (M = Cd Zn) has been reported as a representative of a new class of bis(ary1oxy)bridged dimer~."~ Apparent and partial molar heat 138 K.R. Adam K. P. Dancey A. J. Leong L. F. Lindoy B. J. McCool M. McPartlin and P. A. Tasker J. Am. Chem. SOC.,1988 110 8471. 139 C. Dietrich-Buchecker J-P. Sauvage and J-M. Kern J. Am. Chem. SOC.,1989 111 7791. 140 J. L. Sessler T. Murai and V. Lynch Znorg. Chem. 1989 28 1333; J. L. Sessler T. Murai V. Lynch and M. Cyr J. Am. Chem. SOC. 1988 110 5586. 141 T. Ozawa A. Hanaki and M. Sano Znorg. Chim. Acta 1989 163 231. 142 M. T. Averbuch-Pouchot 2.Anorg. Allg. Chem. 1989 570 138. 143 P. S. Marchetti S. Bank T. W. Bell M. A. Kennedy and P. D. Ellis J. Am.Chem. SOC.,1989 111,2063. M. L. Steigerwald A. P. Alivasatos J. M. Gibson T. D. Hams R.Kortan A. M. Thayer T. M. Duncan D. C. Douglass and L. E. Brus J. Am. Chem. SOC. 1988 110 3046. 145 J. G. Brennan T. Siegrist P. G. Carroll S. M. Stuczynski L. E. Brus and M. L. Steigerwald J. Am. Chem. SOC 1989 111 4141. 146 G. J. Meyer G. C. Lisensky and A. B. Ellis J. Am. Chem. SOC. 1988 110 4914. 147 G. J. Meyer L. K. Leung J. C. Yu,G. C. Lisenski and A. B. Ellis J. Am. Chem. Soc. 1989 111 5146. 148 K. Moller M. M. Eddy G. D. Stucky N. Herron and T. Bein J. Am. Chem. SOC. 1989 111 2564. 149 N. Herron Y. Wang M. M. Eddy G. D. Stucky D. E. Cox K. Moller and T. Bein J. Am. Chem. SOC.,1989 111 530. 150 S. Baral and J. H. Fendler J. Am. Chem. SOC.1989 111 1604. 151 B. R. Eggins J. T. S. Ervine E. P. Murphy and J. Grimshaw J. Chem. SOC.,Chem. Commun. 1988,1123. 152 T. Shiragami C. Pac and S. Yanagida J. Chem. SOC.,Chem. Commun. 1989 831. 153 J. Kallitsis E. Koumanakos E. Dalas S. Sakkopoulos and P. G. Koutsoukos J. Chem. SOC. Chem. Commun. 1989 1146. 154 J. P. Szabo and M. Cocivera Can. J. Chem. 1988 66 1065. 155 D. Coucouvanis K. Greiwe A. Salifoglou P. Challen A. Simopoulos and A. Kostikas Znorg. Chem. 1988 27 593. Zn,Cd Hg 69 capacities and volumes for aqueous Cd" and Hg" EDTA complexes have been deterrni~~ed.''~ The synthesis and structure of M(03PR).H20 and M( HO,PR) (M = Cd Zn; R = n-alkyl) have been de~cribed.'~~ A study of the nature and stability of Cd complexes with the ligands Ph2PCH2P(E)Ph2 and Ph,P(E)CH,(E)PPh (E = S Se) has been described using multinuclear NMR (l13Cd 31P and 77Se) and electrochemical method^."^ A general preference of Cd for S and Se donors versus P was detected.A study of binary and tertiary complexes of Cd" with halide ions and 2,2-bipyridine in DMF has ap~eared.''~ Several studies on thiolato cadmium complexes have been reported. The structure of the mono- nuclear sterically hindered thiolato complex (Et,N),[Cd( SC6H4-0SiMe3),] has been reported.16' Solution equilibrium studies of Cd" complexes of 3-dimethylamino- 1 -propanethiol and comparative studies on other aliphatic y-mercapto amines have appeared.161 The structure of [Cd17S4(SPh)28]2- the 1st member of a 3rd series of tetrahedral [Cd,S,(Sr),]'- clusters has been described.'62 Stability constants of polymeric Cd" complexes of 2-aminopropanethiol have been determined.163 NMR studies '13Cd 199Hg and 31P on Cd and Hg 1,l-dithiolate complexes; [M(S-S),](S- S = S,COPr' S2P(OPri), and S2CNEt, M = Hg) and [M(S-S),]-(S-S = S,CNEt, M = Cd) have been ~ep0rted.l~~ Infra-red and NMR characterization of [M(S-S),]-(S-S = series of N-alkyldithiocarbamates M = Cd Zn) has also been de~cribed.'~' Halogen and psuedohalogen substitution for EPh in some adaman- tanoid chalcogenate clusters [(MEph),(~-Eph)~] (M = Cd Zn; E = S Se) using MeHg+ has been studied with the aid of 77Se and 199Hg NMR.'66 The structure of has been re~0rted.l~~ (Et4N)[Cd(CH30CH2CH20CS2)3] The effect of ClO, BF, and PF anions on the generation of reactive Cd2+ cations via oxidation of CdHg in a non-coordinating medium has been investigated.I6* Reactive Cd2+ generated in CH2C12 via oxidation of CdHg has found use in assessing the donor strength and coordination chemistry of various solvents.169 Migration reactions of organocad- mium and zinc complexes with a-halo-organolithiums have ,been st~died.'~' Cad- mium-metal mediated allylation reactions of carbonyl compounds have been de~cribed.'~' Three-coordinated Cd has been detected in the first cadmium dior- ganophosphide complex; [CH3Cd(p -Bu\P)] synthesized as a precursor for MOCVD.17 The structure of the trinuclear halobridged complex [Li(t.h.f.),]-156 J.K. Hovey and L. G. Hepler Inorg. Chem. 1988 27 3442.157 G. Cao H. Lee V. M. Lynch and T. E. Mallouk Inorg. Chem. 1988 27 2781. lS8 A. M. Bond R. Colton J. Ebner and S. R. Ellis Inorg. Chem. 1989 28 4509. 159 S. Ishiguro K. Ozutsurni M. Miyauchi and H. Ohtaki Inorg. Chem. 1989 28 3258. 160 E. Block M. Gernon H. Kang G. Ofori-Okai and J. Zubieta Inorg. Chem. 1989 28 1263. 161 P. Gonzales-Duarte and J. Vives Inorg. Chem.,' 1989 28 25. 162 G. S. H. Lee D. C. Craig I. Ma M. L. Scudder T. D. Bailey and I. G. Dance J. Am. Chem. SOC. 1988 110 4863. 163 P. Gonzales-Duarte and J. Vives J. Chern. Sor Dalton Trans 1989 13. 164 B. F. Abraharns G. Winter and D. Daketernieks Inorg. Chim.Acta 1989 162 211. I65 A. Frigerio B. Halac and M. Perec Inorg. Chim.Acta 1989 164 149. I66 P. A. W.Dean and J. J. Vittal Can J. Chem. 1988 66 2443. 167 B. F. Abraharns B. F. Hoskins G. Winter and E. R. T. Tiekink Inorg. Chim. Acra 1988 150 147. 168 A. M. Bond S. R. EJlis and A. F. Hollenkarnp J. Am. Chern. SOC.,1988 110 5293. 169 A. M. Bond and S. R. Ellis J. Chem. SOC. Dalton Trans 1988 2379. 170 E. Kegishi and K. Akiyoshi J. Am. Chem. SOC.,1988 110 646. 171 S. Araki H. Ito and Y. Butsugan J. Organomet. Chem. 1988 347 5. 172 B. L. Benac A. H. Cowley R. A. Jones C. N. Nunn and T. C. Wright J. Am. Chem. SOC.,1989 111 4986. D. T. Richens [{Cd(SiMe3)3}3(p-Br)3(p3-Br)]has been re~0rted.l~~ A thermochemical study of heterocyclic N-oxide ligand adducts with Zn Cd and Hg chlorides has appeared.174 The use of Cd(CF3)2 and Cd(CF3)I as 'one-pot' trifluoromethylating agents for the synthesis of other CF3-coordinated metal complexes (e.g.M = Fe Cu) has been rep~rted.'~'The selective chelation of Cd" by quinaldic acids has been studied as demonstrated by the structure of the &coordinate Cd complex (Cd(C18H12N04)2(Me2S0).2H20 (Figure 2).'76 O(3') " Figure 2 The co-ordination polyhedron at cadmium (Reproduced by permission from J. Chem. Soc. Chem. Commun. 1988 810) Mixed ligand Cd" halide complexes with 0ct:PO and pyridine (substituted pyridines) have been studied in 1,2-di~hloroethane.l~~ A 'I3Cd NMR study of the substitution of DMSO by nonaimidodiphosphoramide in solvates of Cd" has appeared.17' Solid state 13Cd NMR chemical shift parameters have been investigated with respect to the complex bis( 2,2'-dipyridylamine- N,N')di(nitrato- O)cadmium(~~).'~~ Stopped-flow kinetic studies of substitution by CN- on bis(4-(2- pyridylazo)resorcinol)cadmium( 11) have been reported."' The effect of C1- media with regard to the solvent extraction of Cd by trilaurylammonium chloride has been investigated.lgl The extraction of Cd" by mixture of organophosphorus compounds has also been reported.Ig2 A full speciation study of the Cd"-diethylenetriamine- 173 N.H. Battrus C. Eaborn M. N. A. El-Kheli P. B. Hitchcock J. D. Smith A. C. Sullivan and K. Tavakkoli J. Chem. SOC.,Dalton Trans. 1988 381. S. A. Al-Juaid N. H. Buttrus C. Eaborn P. B. Hitchcock J. D. Smith and K. Tavakkoli J. Chem. SOC.,Chem. Commun. 1988 1389. 174 M.L. C. P. de Silva A. P. Chagas and C. Airoldi J. Chem. SOC.,Dalton Trans. 1988 2113. I75 (a) W. Dukat and D. Naumann J. Chern. SOC.,Dalton Trans. 1989 739; (b) M. A. Willen-Porada D. J. Burton and N. C. Baenziger .I. Chem. SOC.,Chem. Commun. 1989 1633; (c) D. Naumann and W. Tyrra J. Organomet. Chem. 1989 368,131. 176 C. Moberg M. Muhammed G. Svensson and M. Weber J. Chem. Soc. Chem. Commun. 1988 810. 177 K. Satoh Y. Takahashi T. Susiki and K. Sawada J. Chem. SOC.,Dalton Trans. 1989 1259. 178 L. Rodehuser T. Chniber P. Robini and J-J Delpeuch Znorg. Chim. Acta 1988 148 227. 179 E. A. H. Griffith H-Y. Li and E. L. Amma Znorg. Chim. Acta 1988 148 203. 180 N. Gupta R. M. Naik and P. C. Nigam Znorg. Chim. Acta 1989 160 103. 181 A. Masana L.L. Nadal and M. Valiente Polyhedron 1988 7 715. 182 I. Casas N. Miralles A. M. Sastre and M. Aguilar PoIyhedron 1989 8 2077. Zn Cd Hg 71 N,N,N',N",N"-pentamethylenephosphonicacid system using 'H and 31P NMR has appeared.ls3 Stability constants and composition of mixed 1,3-diaminopropane- malonate complexes of Cd" have been studied by stationary electrode voltammetry at mercury. lS4 The structure of bis( 1,3-bis-hydroxyphenyI)- 1,3-propanedione) bis- pyridinecadmium (11) has been reported."' The structure of tetrameric [C6F5CdOHI4 has appeared. A study of chloride and fluoride complexes of Cd" in aqueous HF media has been reported.'86 Calorimetric and Raman spectroscopic studies of Cd-SCN- complexes in DMF have appearedlS7 as has an X-ray diffraction study of the hexasolvated cadmium( 11) and tetrahedral [Cd( NCS)4]2- complexes in DMF.'" A novel planar polymeric structure occurring in bis(benzy1amine) bis(thiocyanato)cadmium(11) has been characteri~ed."~ The structures of (%N)- [Cd(SCN),] (R = ethyl and n-propyl) have revealed &coordinated cadmium having both N-bonded and S-bonded NCS- ligands.'" In the cases where three N-bonded and three S-bonded NCS- ligands are present the N-bonded ligands were found to be always arranged facially to each other.3 Mercury Mercury(r).-The photooxidation of [Hg(OH2)J+ has been studied.'" Total press- ure measurements have been used to measure the thermal decomposition of mercury (I) halides.'92 The tetrahedrally-coordinated [Hg3C14]+ cation has been characterized in [Hg3C1,][ Ni( aet)3].4H20 (aet = 2-amin0ethanethiolate).'~~ Mercury(rI).-A review of free radical reactions of organomercurials has appeared.'94 Reactions of alkymercurials with heteroatom centred acceptor radicals have been de~cribed."~ Hg(CF3S03)2 has been used to measure the molar AG of transfer for Hg" from acetonitrile into other non-aqueous Standard enthalpies of formation for both inorganic and organometallic complexes of Hg" and Zn" have been disc~ssed.'~' The use of naphthylmercury in transmetallation reactions has been reported as has the synthesis of arylthallium compounds using other organomer- ~uria1s.l~~ Polymeric pentamethylcyclopentadienylmercury(I1) chloride; [Cp*HgCI)] has been found to possess an unusual 'battlement-like' struct~re.'~~ 183 R.D. Gillard P. D. Miralles A. M. Sastre and M. Aguilar Polyhedron 1989 8 2077. 184 H. M. Killa Polyhedron 1989 8 2299. 185 J. Casabo J. Calorner A. Llobet F. Teixador E. Molins and C. Miravitlles Polyhedron 1989,8 2743. 186 R. Beaudoin and H. Menard Can. J. Chem. 1988 66 236. 187 S. Ishiguro T. Takarnuku and H. Ohtaki Bull. SOC.Chem. Japan 1988 61 3901. 188 K. Ozutsumi T. Takarnuku S. Ishiguro and H. Ohtaki Bull. SOC.Chem. Japan 1989,62 1875. I89 A. Ouchi and M. Taniguchi Bull. SOC.Chem. Japan 1988 61 3347. 190 M. Taniguchi and A. Ouchi Bull. SOC.Chem. Japan 1989 162 169. A. Vogler and H. Kunkely Znorg. Chim. Acta 1989 162 169. H. Oppermann C. Barta and J. Tmka Z. Anorg. Allg. Chem.1989 568 187. M. G. W. Van Diepen R. A. G. De Graaff F. B. Halsbergen and J. Reedijk Inorg. Chim. Acta 1989 191 192 193 162 271. 194 J. Barluenga and M. Yus Chem. Rev. 1988 88 487. 195 G. A. Russell P. Ngoviwatchai H. I. Tashtoush A. Pla-Dalrnau and R. K. Khanna J. Am. Chem. SOC. 1988 110 3530. 196 G. Gritzner and G. Krarnl Inorg. Chim. Acta 1989 56 424. 197 J. A. Martinho-Simoes C. Teixeira C. Airoldi and A. P. Chagas J. Organomer. Chem. 1989,361 319. 198 E. Wehman G. Van Koten J. T. B. H. Jastrzebski H. Ossor and M. Heffer J. Chem. SOC.,Dalton Trans. 1988 2975. 199 J. Lorbeth T. F. Berlitz and W. Massa Angew. Chem. Zntl. Ed. Engl. 1988 27 611. 72 D. T Richens [HgPhz.2{ Hg( SCN),( PPh,),}] forms an unusual lattice structure containing both 2 and 4-coordinate mercury.200 The structure of tetrameric 2-pyridylphenylmercury( 11) chloride has been presented.201 The remarkable thermal stability shown by benzyl [tris( dimethylphenylsilyl)] methylmercury is believed to arise from its steric bulk.202 Organomercury complexes of Kojic acidzo3" and malt01~~~' have been characterized.Vibrational spectra and force field calculations on isolelectronic C( HgCH,) and [C(HgNH3),I4+ have been describedzo4 as have force constant calculations on chloromethyl- and bromomethylmercury halide^.^" The use of Hg(CH2C1)2206 and Hg(CF3)2207 as sources of CH2Cl and CF in the synthesis of other organometallic derivatives has been reported. The mercuration of biphenylene radical cation has been reported.208 The synthesis and structure of bis (2,4,6-trichlorophenoxymethyl) mercury has appeared.209 An MNDO study of u-7~interactions in 0-bonded allylmercury compounds has been described.210 An ESR study of the dibenzylmer- cury radical cation has appeared.211 The mode of bonding in nitrosoarene complexes of Hg" has been discussed.212 An adduct formed between diphenylmercury and 1,2-bis(diphenylphosphinothioyl)ethanehas been described.213 Detailed studies regarding organic syntheses using Hg-photosensitized dehydrodimerization have appeared.214 The structures of Hg[N(CF,)SF,] and Hg[ N(CF,)TeF,] have been found to reveal a linear N-Hg-N bond and planar geometry around the N atom.215 Vapour phase absorption spectra and solution MCD and absorption spectra for dihalo and halomethylmercury derivatives have been A binuclear methylmercury complex containing a bridging bismuthiol (2,5-dimercapto-l,3,4- thiodiazole) ligand has been ~haracterized.~" The interaction of CH,Hg+ with cyclopentanesemicarbazone has been describedz1' as has the kinetics involved with the fast ligand exchange on methylmercury( 11) complexes of nitrothi~phenolate.~~~ 2oo T.S. Labana M. K. Sandhu D. C. Povey G. W. Smith and V. Ramdas J. Chem. SOC.,Dalton Trans. 1989 2339. 201 E. C. Constable T. A. Leese and D. A. Tocher J. Chem. SOC.,Chem. Commun. 1989 570. 202 C. Eaborn K. L. Jones J. D. Smith and K. Tavakkoli J. Chem. Soc. Chem. Commun. 1989 1201. 203 S. Bhatia N. K. Kaushik and G. S. Sodhi (a) J. Coord.Chem. 1988 16 311; (b) Bull. SOC.Chem. Japan 1989 62 2693. 204 R. Neufert D. K. Breitinger and J. Mink J. Organomet. Chem. 1988 339 23. 205 M. D.Armitage H. G. M.Edwards and V. Fawcett J. Organomet. Chem. 1989 371 1. 206 R. McCrindle G. J. Arsenault R. Farwaha A. J. McAlees and D. W. Sneddon J. Chem. SOC.,Dalton Trans. 1989 761. 207 D. A. Saulys J. Castillo and J. A. Morrison Znorg. Chem. 1989,28,1619.E. A. Ganja G. D. Ontiveros and J. A. Morrison Znorg. Chem. 1988 27 4535. 208 J. L. Cortneidge A. G. Davies D. C. McGuchan and S. N. Yazdi J. Organomet. Chem. 1988 341 63. 209 G. B. Deacon B. M. Gatehouse and S. C. Ney J. Organomet. Chem. 1988 348,141. 210 K. Y. Burshtein A. N. Isaev and P. P. Shorygin J. Organomet. Chem. 1989 361 21.'11 C. J. Rhodes and H. A. Agirbas J. Organomet. Chem. 1989 378 303. 212 G. Vasapollo C. F. Nobile A. Sacco B. G. Gowenlock L. Sabbatini C. Malitesta and P. Zambonin J. Organomet. Chem. 1989 378 239. 213 T. S. Lobana M. K. Dandhu and E. R. T. Tiekink J. Chem. Soc. Dalton Trans. 1988 1401. 214 S. H. Brown and R. H. Crabtree J. Am. Chem. SOC.,1989 111 2935. 21s J. S. Thrasher J. B. Neilson S. G. Bott D. J. McClure S. A. Morris and J. A. Atwood Znorg. Chem. 1988 27 570. 216 M. M. Savas and W. R. Mason Znorg. Chem. 1988 27 658. 217 M. V. Castano M. M. Plasencia A. Macias J. S. Casas J. Sordo and E. E. Castellano J. Chem. SOC. Dalton Trans. 1989 1409. 218 A. Macias M. C. Rodrigues-Arguelles M. I. Suarez A. Sanchez J. S. Casas J. Sordo and U.Englert J. Chem. SOC.,Dalton Trans. 1989 1787. 219 G. Geier and H. Gross Znorg. Chim. Acta 1989. 156 91. Zn,Cd,Hg Figure 3 StmCfUre Of [{ Hg3CO(C,H6N0)6}( NO,),] (Reproduced by permission from Angew. Chem. In?. Ed. Engl. 1988 27 261) The structure of [{Hg3Co(C4H6NO)6}( NO,),] (Figure 3) a macrobicyclic bimetallic chain polymer incorporating deprotonated 2-pyrrolidone bridges has appeared220" showing evidence for two distinct Hg environments coordinated to N. The nature of the NO ions being loosely bound in channels away from the Co centre have led to further investigations of these compounds as a possible new class of anion-exchange polymer. The structures of the mixed-metal complexes [Hg2EuL4-(Nod31n ,220b [Hg3n2L6(No3)61 n ,220b [H~3Zn2L6(N~3)3.33(0cH3)0.6i'~ n ?,OC and [Hg2L2C12]~20c = 2-pyrrolidone anion) have also been reported.[HgCuL',(N03)- (L (OCH3)] (L' = 3-methyl-2-pyrrolidonate) however has a dimeric structure.220d NMR( 199Hg 31P and 77Se) and electrochemical studies of non-labile Hg" complexes containing the ligands Ph2PCH2P(E)Ph and Ph,P(E)CH,P(E)Ph (E = S Se) have appeared2,' as have 199Hg 31P 77Se and '25Te NMR studies on the tellurato-bridged adamantane-like Hg" cage clusters; [(p-TeR),( HgPR$)4]2+ and [(p-TeR),-Hg(HgPR;),l2+ (R = Me Ph; R' = Ph 4-C6H,Me and 4-C6H4C1).,, Studies involving 199Hg 'H and I3C NMR on amine complexes of the type (R'R2CH- NHR),HgCl have also been reported.223 The synthesis and structures of [Hg(C5H4NS)(CH3C02),ln Hg(C5H4NS)2 and Hg(CH2P(S)Ph)2(C5H4NS = 2-mercaptopyridine) having one-dimensional chain structures have been described.224 Spectroscopic and INDO studies on bis( 2-amino-5-methyl- 1,3,4-thiadiazole-N,) dibromomercury(11) have been reported.225 Pentagonal 220 D.M. L. Goodgame D. J. Williams and R. E. P. Winpenny (a) Angew. Chem. Int. Ed. Engl. 1988 27 261; (b) J. Chem. SOC.,Dalton Trans. 1989 1439 and J. Chem. Soc. Chem. Commun. 1988 437; (c) Polyhedron 1989 8 1913; (d) ibid. 1989 8 873. A. M. Bond R. Colton and J. Ebner Inorg. Chem. 1988 27 1697. P. A. W. Dean V. Manivannan and J. J. Vittal Inorg. Chem. 1989 28 2360. 221 222 223 S. AI-Showiman Inorg. Chim. Acta 1988 141 263. 224 S. Wang and J. P. Fackler Inorg. Chem. 1989 28 2615. 74 D.T. Richens bipyramidally coordinated Hg" has been found in the structure of [HgL][ HgCI,] L = 2,6-diacetylpyridine bis(2'-pyridylhydrazone).226 Several studies with regard to halomercury(I1) complexes with tertiary phosphines have a~peared.,~~-~*~ The structure of phenyl( triphenylphosphino)mercury( 11) nitrate has been discussed2" as has the synthesis and structure of [bis(p-sulphato)tris(p-bisdiphenylphos-phino)methane]triang~lo-trimercury.~~~ Hg12( PPr,) has been found to contain an unsymmetrical I,Hg( ~-1)~Hg( PPr,) arrangement.230 X-ray scattering and Raman studies on [Hg21l3+ in DMSO and water have shown the angle at I to be 89°.231 Vibrational spectra and thermal analysis on Hg" complexes of dithiooxamide have been Stable Hg atoms can be generated under ambient conditions via photoredox reactions on triazidomercury (11) .233 Isoconcentration functions have been used to measure stability constants of protonated 1,2-diaminoethane complexes of Hg".234 Assembly disassembly and reassembly of Hg,Co,(CO) ,' has been described235 as have 199Hg NMR studies on several other Hg-bridged transition metal clusters.236 31P CP-MAS NMR IR and Raman studies on HgLX2 (L = 1,3,5-triaza-7-phosphaadamantane, X = C1- Br- I- SCN- CN- and NO;) have been reported.237 The structure of 1,8-dihydroxy-3,6-dithiaoctane bismercury(11) chloride has appeared.,,' AM 1 calculations for various mercury compounds have been Bioinorganic and Biological Mercury.-A metallothionein bound by 18 Hg atoms has been characterized from rabbit liver.240 13C NMR studies of thiol ligand exchange on Hg" complexes of glutathione cysteine and penicillamine have appeared.241 X-ray absorption studies of Hg substitution at type 1 Cu sites have been Methylmercury(I1) complexes with 7-meth~lguanine,~~~ 8-3-meth~ladenine,~~ a~aadenine,~,~ 9-meth~l-S-azaadenine,~~~ 7-dea~a-g-azaadenine,~,~ 4-225 L.Antolini A. Benedetti A C. Fabretti A. Giusti and M. C. Menziani J. Chem. SOC.,Dalton Trans. 1988 1075. 226 G. Chessa G. Marangon B. Pitteri V. Bertolasi V. Ferretti and G. Gill J. Chem. SOC.,Dalsfon Trans. 1988 1479. 227 N. A. Bell L. A. March and I. W. Nowell Inorg. Chim. Acfa 1989 156 195 and ibid. 1989 162 57. 228 T. S. Lobana M. K. Sandhu D. C. Povey and G. W. Smith J.Chem. SOC.,Dalton Trans. 1988 2913. 229 B. Hammerle E. P. Muller D. L. Wiikinson G. Muller and P. Peringer J. Chem. SOC. Chem. Commun. 1989 1527. 230 N. A. Bell N. A. Chudley L. A. March and I. W. Nowell Inorg. Chim. Acfa 1988 141 155. 23 1 L. Bengtsson B. Holmberg I. Person and A. Iverfeldt Inorg. Chim. Acfa 1988 146 233. 232 P. Geboes and H. 0.Desseyn Chim. Acta 1989 161 169. 233 H. Kunkely and A. Vogler Polyhedron 1989 8 2731. 234 M. Wilgocki J. Coord. Chem. 1988 16 357. 235 J. M. Ragosta and J. M. Burtlitch Organometallics 1988 7 1469. 236 E. Rosenberg J. Wang and R. W. Gellert Organomefallics 1988 7 1093; S. Hajela E. Rosenberg R. Gobetto L. Milone and D. Osella J. Organomef. Chem. 1989 377 85. 237 E. C. Alyea K. J. Fisher and S.Johnson Can. J. Chem. 19S9,67 1319. 238 J. Sieler U. Braun B. Eulitz and E. Hoyer Z. Anorg. Allg. Chem. 1988 566 131. 239 M. J. S. Dewar and C. Jie Organometallics 1989 8 1547. 240 W. Cai and M. J. Stillman J. Am. Chem. SOC. 1988 110 7872. 241 B. V. Cheesman A. P. Arnold and D. L. Rabenstein J. Am. Chem. SOC.,1988 110 6359. 242 A. Schmidt-Klemens D. R. McMillan H.-T. Tsang and J. E. Penner-Hahn J. Am. Chem. SOC.,1989 111 6398. 243 W. S. Sheldrick and P. Gross Inorg. Chim.Acfa 1988 153 247. 244 W. S. Sheldrick and H. Gross Inorg. Chim. Acta 1989 156 91. 245 W. S. Sheldrick and P. Bell Inorg. Chim.Acfa 1989 160 265. 246 W. S. Sheldrick P. Bell and H.-J. Hausler Inorg. Chim. Acra 1989 163 181. Zn Cd Hg nitroimida~ole,~~' and have been discussed.Binary and tertiary complexes of d-valine and various uracils with Hg" have been described.249 A biomimetic synthesis of troponone via oxidation of hygrine with mercury(1r) acetate has been ~haracterized.~~' Macrocyclic Chemistry.-Studies on porous,251 cohesive,25' and perforated252 monolayers resulting from mercuration of calix-[ n]-arenes have been described. [Hg( diamsar)12+ and [Hg( diamsarH2)I4+ have been used to study the in-plane packing of pillars in ~mectites.~~~ The Hg salt trapping ability of tropanoid-annexed dithio crown ethers has been The structure of [Hg([9]aneS,)2](PF& has appeared.255 A full complexation study of the interaction of Hg" ions with macromonocyclic 16-membered dioxopentamine and 18-membered dioxohexamine ligands has been reported.256 The preparation and characterization of two classes of Hg-bridged bimetallocyclic donor ligand has appeared.257 Solid State Chemistry.-A review concerned with two-dimensional condensation at the Hg-H20 'dynamic double layer' interface has appeared.258 Attempts to rational- ize the types of Hg polyhedra in Hg-metal clusters and amalgams have been Uniquely formed Hg cubes in addition to Hg rectangles have been detected in Rb15Hgl .260 A new procedure to semi-conductor quality HgTe using phosphinetellurides has been described.261 Experiments and calculations with regard to the chemical transportation of W02 W03 ,262a,b and W18049262b on mercury( 11) halides have been reported.247 A. R. Norris R.Kumar and A. L. Beauchamp Inorg. Chim. Acra 1989 162 139. 248 M.-C. Corbeil and A. L. Beauchamp Can. J. Chem. 1988 66 1379. 249 R. M'Boungou M. Petit-Ramel G. Thomas-David G. Perichet and B. Pouyet Can J. Chem. 1989 67 973. 250 E. Leete and S. H. Kim J. Chem. Soc. Chem. Commun. 1989 1899. 25 1 M. A. Markowitz R. Bielski and S. L. Regen J. Am. Chem. Soc. 1988 110 7545. 252 M. A. Markowitz V. Janout D. G. Castner and S. L. Regen J. Am. Chem. Soc. 1989 111 8192. 253 F. Tsvetkov and J. White J. Am. Chem. Soc. 1988 110 3183. 254 H. Takeshita A. Mori and S. Hirayama J. Chem. SOC.,Chem. Commun. 1989 564. 255 A. J. Blake A. J. Holder T. I. Hyde G. Reid and M. Schroder Polyhedron 1989 8 2041. 256 M. Kodama and E. Kimura Bull. Soc. Chem.Japan 1989 62 3093. 257 A. L. Balch M. M. Olmstead and S. P. Rowley Znorg. Chem. 1988 27 2275; R. Richter J. Sieler R. Kohler E. Hoyer L. Beyer I. Leban and L. Golic Z. Anorg. AlIg. Chem. 1989 578 198. 258 R. delevie Chem. Rev. 1988,88 599. 259 R. B. King Polyhedron 1988 7 1813. 260 H.-J. Deiseroth and A. Strunck Angew. Chem. Zntl. Ed. Engl. 1989 28 1251. 26 L M. L. Steigerwald and C. R. Sprinkle Organometallics 1988 7 245. 262 H. Schornstein and R.Gruehn (a) Z. Anorg. Allg. Chem. 1988 556 240; (b)ibid. 1989 579 173.

ISSN:0260-1818    

DOI:10.1039/IC9898600061

出版商:RSC    

年代:1989

数据来源: RSC

摘要:

6 Sc Y the Lanthanides and the Actinides By C.J. JONES School of Chemistry University of Birmingham Edgbaston Birmingham B 15 27T 1 Introduction The arrangement of this Chapter is broadly similar to that used in previous years so that following this introduction there are three main sections. The first of these is concerned with scandium and the second with yttrium and the lanthanides. This latter section is subdivided under the topic headings ‘Oxides and Solid State Studies’ ‘Catalysts and Reagents* ‘Solution Studies* ‘Luminescence Studies’ ‘Coordination Compounds* and ‘Organolanthanide Compounds*. The third and final section on the actinide elements is subdivided under the headings ‘General and Coordination Chemistry’ and ‘Organoactinide Chemistry’. The emphasis in this report has been placed primarily on molecular species and following the precedent of previous years papers relating solely to stability constant measurements and studies of binary or ternary compounds have in the main not been included.During the year there have been two additions to Gmelin’s Handbook of Inorganic Chemistry which relate to f-block elements. The first of these is entitled ‘Alloys of Uranium with Alkali Metals Alkaline Earths and Elements of Main Groups I11 and IV’ and describes alloys and intermetallic compounds of uranium formed with some main group elements.’ Binary and some ternary systems are covered and there is a chapter on UBeI3. Cermets and alloys of the U-Alsystem important in high neutron flux research reactors are also included.The second volume is entitled ‘General Properties Spectra and Recoil Reactions’ and brings together the proper- ties of thorium including electronic structure ionic radii and ionization potentiak2 Thermodynamic properties recoil reactions and the effects of ionizing radiation on thorium alloys are also covered. Although not strictly associated with the f-block elements a book has appeared which considers the theoretical bases for predicting the stabilities of superheavy elements and the approaches used for their preparati~n.~ The design and synthesis of lanthanide(II1) complexes with 18-membered ring N,-macrocycles has been re~iewed.~ Reviews have also appeared on the preparation structures and properties of the actinide^,^ on the coordination compounds of Np Gmelin Handbook of Inorganic Chemistry 8th Edn.U-Uranium Supplement Vol. B2 Springer-Verlag Berlin 1989. * Gmelin Handbook of Inorganic Chemistry 8th Edn. Th-Thorium Supplement Vol. B4 Springer-Verlag Berlin 1989. K. Kumar Superheuuy Elements Hilger Bristol 1989. M. L. Vallarino J. Less-Common Met. 1988 149 121. M. Beauvy and J. Larroque J. Nucl. Muter. 1989 166 83. 77 78 C.J. Jones and PU,~ and on the thermodynamic properties off-element hydroxides and oxide~.~ A review of the theoretical and experimental data pertaining to the extent of covalency in f-element organometallic compounds indicates that ligand-metal orbital overlap considerations are important in rigorous descriptions of their electronic structures.' However they are rarely manifest in the chemical behaviour of the compounds.Compounds of Th and U in low ( <IV) oxidation states have also been reviewed.' Two new developments during the year are the first report of a lanthanide dihydrogen complex and the first report of a direct high resolution n.m.r. observation of an f-block element. The shift and line shape of the resonance of H2 dissolved in C6D12 change upon the incremental addition of EuCpf (Cp* = v5-C5Me5). This observation is interpreted in terms of EuCpS( q2-H2) formation." 171Yb n.m.r. spectra of YbCp?(OEt,) Y~CP,*(NC~H~)~, Yb(NR2)2(OEt2)2 (R = SiMe,) Yb(NR2)2(P-NR2)2Na [Yb"R2)(P-NR2)212 [Yb(NR,),(Me2PCH2CH2PMe2)1 and YbCp?(t.h.f.) have been obtained and the spectrum of Yb(NR2),(OEt2)2 reveals a 171Yb-14N coupling constant of 118Hz." The continuing interest in the preparation of superconducting materials incor- porating yttrium or lanthanide elements is stimulating work on alkoxide complexes as components of possible molecular precursors to superconducting materials.In a more general context a review of the use of metal alkoxides as precursors to ceramic or electronic materials has appeared.12 This describes MOCVD and Sol-gel processes and the production of volatile mixed metal alkoxide derivatives. In the medical sphere the use of Gd3+ as a contrast agent in diagnostic Magnetic Resonance Imaging is encouraging work on new coordination complexes of Gd3+ which may exhibit favourable biodistribution proper tie^.'^ Also of medical interest is the development of a system for attaching 90Yto antibodies to provide a radiotherapy agent.14 2 Scandium A prominent topic among the few publications dealing with scandium has been its interaction with small molecules.A theoretical model of CO binding to Sc+ indicates that the bonding is electrostatic in nature with no more than 10% ligand to metal a-donation and essentially no metal to ligand donation.'^ The calculated C-Sc+ distance is 2.38 A. The X-band e.s.r. spectrum of ScCO at 4 K indicates that a 41; ground state is present with a low lying 411excited state in general accord with ab initio calculations.'6 Guided ion beam mass spectrometry has been used to examine N. N. Krot and D. N. Suglobov Radiokhimiyu 1989 31 1. ' T.Sato Thennochim. Actu 1988 (Publ. 1989) 149 249. J. C. Burns and B. E. Bursten Comments Inorg. Chem. 1989 9 61. I. Santos and A. fires de Matos Adv. Inorg. Chem. 1989 34 65. 10 S. P. Nolan and T. J. Marks J. Am. Chem. Soc. 1989 111 8538. A. G. Avent M. A. Edelman M. F. Lappert and G. A. Lawless J. Am. Chem. Soc. 1989 111 3423. 12 D. C. Bradley Chem. Rev. 1989 89 1317. l3 P. H. Smith J. R. Brainard D. E. Moms G. D. Jorvinen and R. R. Ryan J. Am. Chem. Soc. 1989 111,7437. 14 J. P. L. Cox K. J. Jankowski R. Kataky D. Parker N. R. A. Beeley B. A. Boyce M. W. Eaton K. Millar A. T. Millican A. Harrison and C. Walker J. Chem. Soc. Chem. Commun. 1989 797. 15 A. Mauridis J. F. Hamson and J. Allison J. Am. Chem. Soc. 1989 111 2482. 16 R. J. Van Zee and W.Welter Jnr. 1.Am. Chem. Soc. 1989 111 4519. 79 Sc Y the Lanthanides and the Actinides the reactions of Sc+ Y+ La+ and Lu+ with CH4 and C2H6.I' The major products with CH are LnCH; at low energy and MH+ at high energy. Fourier transform mass spectrometry has been used to study the chemistry of FeSc+ which was reactive towards alkenes but not alkanes." With alkenes C-H bond activation predominates over C-C activation. Two studies of aquated Sc3+ complexes have been carried out. Aqueous solutions of Sc3+ at ca. pH4 have been shown by 45Sc n.m.r. to contain Sc(H20):+ Sc( H20)5(0H)2' and Sc2( H20)8(OH):+ as the dominant species." 45Sc n.m.r. studies of the interaction between Sc(OH)2+(aq) with serine and small peptides were also carried out.Crystals of [{SC(OH,)~)~(~-OH)~](P~SO~)~.~H~O contain seven-coordinate Sc3+ ions in a pentagonal bipyramidal coordination geometry.20 The momomer units are joined through bridging OH ligands occupying adjacent equatorial sites in the edge linked bipyramids. The additional five H20 ligands on each Sc complete the coordination sphere. In the organometallic sphere the complexes ScCpTR (R = H Me) react with MCp2(CO) (M = Mo W; Cp = v5-C5H5) to give C~,M=C(R)OSCC~?.~~ The reaction of ScCpf Me with COC~(CO)~ affords CoCp(p2,v1,v1-CO)[ =C( Me)OScCp;] which contains an almost planar six-membered -Co-C-0-Sc-0-C(Me)-ring. Complexes of scandium with cyclo-octatetraenyl ligands carrying sterically-bulky substituents have also been reported. Thus 1,4-(Me3Si)2C8H$- has been found to react with ScCl,(t.h.f.) to give {Sc[1,4- (Me3Si)2C8H6]( ~-Cl)}~(p-t.h.f.) the X-ray crystal structure of which reveals a semi-bridging t.h.f.ligand (Figure 1).22 CB 1) Figure 1 The structure of {Sc[(l,4-Me,Si),C,H,](p-Cl)}2(p-t.h.f.) Sc(1)-0 = 3.056(9) and Sc(2)-0 = 2.324(7)A (Reproduced by permission from J. Chem. SOC.,Chem. Commun. 1989 1462) 17 L. S. Sunderlin and P. B. Armentrout J. Am. Chem. SOC.,1989 111 3845. 19 L. M. Lech J. R. Gord and B. S. Freiser J. Am. Chem. SOC.,1989 111 8588. l9 D. Rehder and K. Hink Znorg. Chirn. Acta 1989 158 265. 2o F. Matsumoto Y. Ohki Y. Suzuki A. Ouchi Bull. Chem. SOC.Jpn. 1989 62 2081. 2' M. A. St. Clair D. Sontarsiero and J. E. Bercaw Organometallics 1989 8 17. 22 M.C. Burton F. G. N. Cloke P. B. Hitchcock H. C. de Lemos and A. A. Sameh J. Chem. SOC.,Cbem. Commun. 1989 1462. C. J. Jones 3 Yttrium and the Lanthanides A new and convenient synthesis of SmBr from Sm203 by reaction with COBr has been de~cribed.,~ The thermodynamically favourable elimination of CO pro- vides a driving force for this reaction. A kinetic study has been carried out to investigate the mechanism of lanthanide oxide chlorination by CCl and some physiochemical properties of PmC1 were predicted on the basis of interp~lation.~~ Fluorination of some lanthanide oxides using ammonium hydrogen fluoride affords (NH,),[LnF,]-nH,O (Ln = Y La Nd and Pr) and (NH,),[CeF,].25 Oxides and Solid State St~dies.-'~O labelling of Y203 has been demonstrated by 17 0 n.m.r.studies2 and an f.t.i.r. study of "0 labelled partially reduced cerium oxide indicates the presence of peroxide and ~uperoxide.~~ The finding that YBa2Cu,07 and La,,8Sro.2Cu0 liberate O2 upon dissolution in acid has been investigated., 'In these cases no evidence was found for the presence of peroxide nor was peroxide detected in La,CuO and La2Ni0,. In L~N~,.,CU~.~O~ core level spectroscopic studies indicate that the excess positive charge is present on oxygen rather than as Cu3+.29 The magnetic structures of Nd,CuO and Nd1.97Ce0.03C~04 have been determined at 1.6 K,30using powder neutron diffraction methods. A lower limit for the Cu ordering temperature was estimated at 170 K. The synthesis of potential superconducting mixed metal oxides continues to be of interest and homogeneous reactions are being used to prepare materials for thermal processing.Superconducting YBa2Cu307- powders have been prepared from aqueous solutions containing Y3+ Ba2+ Cu2+ and oxalic acid by homogeneous co-precipitation using urea.31 Calcination of the precipitate at 900 "C for 16 h followed by sintering at 950 "C for 16 h gave a material with T = 93 K. The copper alkoxides Cu(OR) [R = CH,CH,OMe CH2CH20CH2CH20Me, and (CH,),Me] have been used in the hydrolytic synthesis of YBa2Cu307- precursors from t.h.f. solutions also containing Ba(OPr') and Y,O(OPr'), .32 Lower formation tem-peratures for YB~,CU,O,-~ are possible from materials prepared by this route.33 X-Ray studies of YSr2Cu307-x YBaSrCu307-, and YC~S~CU,O~-~ suggest that Ca2+ ions are too small to lead to structures giving supercond~ctivity.~~ Several other mixed metal oxide systems have been described.(SrLa)(MoO,) is a complex perovskite which contains MOO octahedra.,' The material is cubic with a0 = 7.932(1) A and shows Curie-Weiss behaviour with peff= 1.72(1) pusconsistent with the presence of Mo" centres. In the complexes K,,[Ln(GaW,,039H2)2].xH20 (Ln = 23 M. J. Parkington K. R. Seddon and T. A. Ryan J. Chem. Soc, Chem. Commun. 1989 1823. 24 D. M. Laptev T. V. Kiseleva V. F. Goryushkin N. M. Kulugin and N. G. Kulagina. Russ. J. Inorg. Chem. 1989 34 27. 25 S. J. Patwe B. N. Wani U. K. Rao and K. S. Venkateswarlu Can. J. Chem. 1989 67 1815. 26 S. Yang K.D. Park and E. Oldfield J. Am. Chem. Soc. 1989 111 7278. 27 C. Li K. Domen K. Maruya and T. Onishi J. Am. Chem. Soc. 1989 111 7683. 28 D. C. Harris and T. A. Vanderah Inorg. Chem. 1989 28 1198. 29 G. R. Rao M. K. Rajumon D. D. Sarma and C. N. R. Rao J. Chem. SOC.,Chem. Commun. 1989,1536. 30 M. J. Rosseinsky K. Prassides and P. Day J. Chem. SOC.,Chem. Commun. 1989 1734. 31 R. S. Liu C. T. Chang and P. T. Wu Inorg. Chem. 1989 28 154. 32 S. C. Goel K. S. Kramer P. C. Gibbons and W. E. Buhro Inorg. Chem. 1989 28 3619. 33 H. S. Horowitz S. J. McLain A. W. Sleight J. D. Pruliner P. L. Gai M. J. Von Kavelaar J. L. Wagner B. D. Briggs and S. J. Poon Science 1989 243 66. 34 G. Nordin L. Rondaccio and E. Zangrando Inorg. Chim. Acta 1989 164 1.3s J. H. Choy and S. T. Hong J. Chem. Soc. Dalton Trans. 1989 2335. Sc Y the Lanthanides and the Actinides 81 La Ce Pr Nd Sm Eu Gd Tb Dy Tm Yb) which have been prepared from K,GaW,,O,, magnetic data are consistent with the presence of Ln3+ ions.36 The syntheses and structures of some tantalum containing compounds have also been described. La3Ta05(OH)Cl and Pr3Ta0,C1 have been prepared by chemical trans- port and studied by high resolution electron Single crystals 'LaTa,O,,' contain layers of composition [Ta22062]14- with holes partially or fully occupied by La3+ ions.38 Reports of compounds with the later transition metals include BaNiDy,05 and BaNiLu,O .39 The former contains nickel in an octahedral coordina- tion environment while the latter belongs to the BaCuLn20s structural series and contains nickel in a tetragonal pyramidal coordination environment.BaCoY20 is also of the BaCuLn,O structural family while BaCoGd20s and BaCoDy20S belong to the BaNiLn205 structural family.,' BaCoHo205 BaCoYb20, and BaCoEr,O have also been ~ynthesized.,~ The first two compounds have the BaCuSm,O,-type structure and the last a BaNiLn,O,-structure. The Dy atoms in Ba,Dy2Al4OI5 have been found42 to have an octahedral coordination environment and the synthesis and structure of Cs2Lil4[Tb3OI4] has been 151 Eu Mossbauer spectra have been reported for EuI,(t.h.f.) [EuCp,(t.h.f.)], [EuCp*(t.h.f.),(p-I)I2 EuCpT EuC~*(t.h.f.)(OEt~).~ Broad absorptions were observed arising from spherical paramagnetic relaxation at a rate approaching the Mossbauer timescale (9.7 x lo- s) except in the case of [EuCp*(t.h.f.)] which exhibited a narrow line spectrum with a quadruple interaction of -12.9 mms-'.A Curie-Weiss temperature of 3.28 K was found for EuCpT. The use of XPS to determine the Ce"'/Ce'v ratio in materials is usually limited by the small magnitude of the shift in binding energy between Ce"' and CeIV. However the use of a modified Auger parameter and the relative 4d,,,/4d,/ peak area ratio allows this ratio to be extracted from the data.45 The magnetic properties of the bis-adducts of {Ln[CF3C(0)CHC(CF3)O]3L}fl(Ln = Eu Gd; L = 1H-imidazoyl-1-oxyl-3-oxide 2-R-4,4,5,5-tetramethyl-4,5-dihydro-radical with R = Ph Et) have been investigated., In the Gd'" complex there is weak ferromagnetic coupling between the radical and the metal.The radicals are antiferromagnetically coupled to one another. Extended Huckel calculations on Er,Rh,Cl indicate that treating Er merely as a three-electron donor does not account for all the geometric features of the structure it is also necessary to include Er atomic orbitals in the P-Ln2C13N (Ln = Y Gd) have been obtained from heating LnCl, LnN and Ln in sealed container^.^' P-Y2C13N contains infinite chains of edge sharing Y octahedra 36 J. Liv Z. Zu B. Zhao and Z. Liu Inorg. Chim. Acta 1989 164 179. 37 B. Langenbach-Kuttert G. Steinmann W. Mertin and R. Gruehn Z. Anorg. Allg. Chem. 1989,573 119. 38 U. Schaffrath and G. Gruehn 2. Anorg. Allg. Chem. 1989 573 107. 39 H.K. Muller-Buschbaum and 1. Reiter 2. Anorg. AIIg. Chem. 1989 572 181 40 H. Mevs and H. K. Muller-Buschbaum 2. Anorg. AIIg. Chem. 1989 573 128. 41 H. Mevs and H. K. Miiller-Buschbaum 2. Anorg. Allg. Chem. 1989 574 172. 42 I. Riiter and H. K. Miiller-Buschbaum Z. Anorg. AIlg. Chem. 1989 573 89. 43 S. Voigt R. Werthmann and R. Hoppe 2.Anorg. Allg. Chem. 1989 574 65. 44 A. F. Williams F. Grandjean G. J. Long T. A. Ulibarri and W. J. Evans Inorg. Chem. 1989 28 4584. 45 C. A. Strydom and H. J. Strydom Inorg. Chim. Acta 1989 161 7. 46 C. Benelli A. Coneschi D. Gatteschi L. Pardi P. Rey D. P. Shum and R. L. Cardin Inorg. Chem. 1989 28 272. 47 S. Lee W. Jeitschko and R. D. Hoffmann Inorg. Chem. 1989 28 4094. 48 H. J. Meyer N. L. Jones and J.D. Corbett Inorg. Chem. 1989 28 2635. C. J. Jones as found in Y2C13 with the nitrogen atoms positioned in tetrahedral metal sites above and below the shared metal edges. Y,I,,Ru which is isostructural with Sc,Cl,,B has been prepared from the reaction between Y,Ru and Y13 at 800- 950 0C.49 The reaction also affords Y6IloRu which contains edge (p-I)bridged Y6II2 clusters centred by Ru and condensed into infinite chains uia bridging iodides (Figure 2). The Y,Ru cluster shows a tetragonal compression of 0.21 8 compared to an idealized octahedron. Calculations indicate that this arises from Y-Y inter- actions. The crystal structures of LaBr, La2Br, and LaBr3 have been determined.50 Figure 2 (a) The (110) section of Y,I,,Ru with the Y-Ru bonds emphasized; (b) A view of approximately normal to that of Figure 2(a) showing the Y,I,,Ru chains (Reproduced by permission from Znorg.Chem. 1989 28 631) T. Hughbanks and J. D. Corbett Inorg. Chem. 1989 28 631. so K. Kramer T. Sahleid M. Schulz W. Urland and G. Meyer Z. Anorg. AIIg. Chem. 1989 575 61. Sc Y the Lanthanides and the Actinides 83 LaBr has the CeCl structure while La2Br is like Pr21s. LaBr crystallizes in a 2H2-MoS type of structure with trigonal prismatically coordinated La atoms and an La-Br distance of 3.07 A. An X-ray structural study of HoAl3ClI2 shows that the Ho3+ ion is eight coordinate with a square antiprismatic arrangement of chloride ligands derived from tetrahedral AlC1 units bound as bidentate ligands in the lattice.,' Catalysts and Reagents.-Work on olefin oligomerization olefin-oxide oligomeriz- ation hydrocarbon coupling hydrogenation and oxidation catalyst systems has appeared.Kinetic stereocontrol in the polymerization of butadiene by an Nd- A1 catalyst system has been in~estigated.~~ The ratio of the formation rates of 1,4-cis and 1,4-trans units depends linearly on the current monomer concentration. The oligomerization of ethene to alkylcyclopentanes and/ or alkylcyclohexanes has been effected using YbCIJAlEtCl as a Ziegler-Natta type catalyst.53 The presence of CO during the reaction is essential otherwise only linear oligomers are obtained. High molecular weight poly(ethy1ene oxide) can be produced from ethylene oxide using the Y[OP(=O)(OCH2CH(Et)CH2Me)2]3/AlBu;/H,0 catalyst system.54 The catalytic activity is highly dependent upon the molar ratio of the three catalyst components.The oxidative conversion of methane to C2 hydrocarbons and the selectivity of this conversion has been found to be sensitive to the distribution of oxygen within La-promoted MgO catalysts.55 An increase in C2 selectivity but a decrease in methane conversion is associated with an increase in the CH4:02 ratio. A deuterium isotope effect has been observed in the coupling of CH4 over a samarium oxide catalyst; making mechanistic interpretations of earlier studies more diffi~ult.~~ Lanthanide promoted hydrogenation catalysts have been prepared from the direct reaction of Fe Ni Cu or Ag powder with Eu or Yb in liquid ammonia." The oxidation of water to O2 by Ce'" in a reaction mediated by thermally activated Ru02.H20* has been the subject of a kinetic This indicates that Ru02-yH20* particles act as microelectrodes through which electrons are irreversibly removed from water then reversibly transferred to Ce'".A synergistic effect on the reactions of CO with O2 and NO with CO is reported when LaMno.6Cuo.403 is used instead of either LaMnO or La2Cu04.59 Interest in the use of lanthanides as reagents to effect organic transformations has continued. The reactions of metallic Ln (Ln = Ce Nd Sm Yb) with olefins and aromatic ketones have been investigated and Yb found to be the most reactive of the metals tested.60 Reduction reactions and the cleavage of C-C and C-0 bonds were observed.The mechanism of formation of 2-benzoyl-1 -phenylpropanol 51 D. Hake and W. Urland Angew. Chem. In!. Ed. Eng. 1989 28 1364. 52 Z. M. Sabirov N. Kh. Minchenkova and Y. B. Monakov Inorg. Chim. Acta 1989 160 99. 53 W. Keim Z. Chen and Z. Chen J. Chem. SOC.,Chem. Commun. 1989 1923. 54 Y. Zhang X. Chen and Z. Chen Inorg. Chim. Acta 1989 155 263. 55 V. R. Choudhary S. T. Choudhari A. M. Pajput and V. H. Rone J. Chem. SOC. Chem. Commun. 1989 1526. 56 A. Ekstrom and J. A. Lopszewicz J. Am. Chem. SOC.,1989 111 8515. 57 H. Imamura T. Mihara M. Yoshinobu Y. Sakata and S. Tsuchiya J. Chem. Soc. Chem. Commun. 1989 1842. 58 A. Mills and S. Giddings Inorg. Chim. Acta 1989 158 49. 59 M. Mizuno Y. Fujiwara and M. Misono J. Chem. SOC.,Chem.Commun. 1989 316. 60 Y. Chauvin H. 0.Rivier and L. Saussino Inorg. Chim. Acta 1989 161 45. C. J. Jones in an LaBr assisted aldol reaction has been investigated.61 The reaction involves an LaBr,:benzaldehyde:t.h.f. complex. In addition CeC1 and LaCl have been found to promote the phase transfer catalysed carbonylation of benzyl bromide.62 Samarium compounds may be employed to effect coupling reactions. Thus Sm12 promotes intramolecular coupling reactions to form functionalized carbocycle~.~~ The electrochemical coupling of carbonyl compounds to give 1,2-diols in high yields is catalysed by SmCl,.64 The addition of CeC1 to Gringard reactions of ketones has been found to suppress side reactions especially enoli~ation.~~ The enantio- selective reduction of ketones (acetophenone octan-2-one and butan-2-one) with NaBH may be achieved using fac-A-tris(4-l-menthyloxy)-l-( p-tolylbutane-1,3-dionato)lanthanoid(rII) (1) as the Lewis acid catalyst.66 Me Me R = I-menthyl Me (1) Solution Studies.-Several spectroscopic studies have utilized Judd-Ofelt theory and the oscillator strengths and Judd-Ofelt parameters (ClA ) for the two hypersensitive -+ transitions of Er"' (4115/2 2H11/4 and 4115,2 + 4G11/2)have been measured and correlated with the induced chemical shift produced by Er"' in n.m.r.studies.67 In another study of the links between the hypersensitive pseudo-quadrupole transition in the electronic spectra of lanthanide ions and the induced chemical shift of lanthanide shift reagents in n.m.r.the oscillator strengths and Judd-Offelt para- meters of Nd(O,CR) (R = CH3 CH2Br) have been determined.68 The absorption 61 A. J. Fry and M. Susla J. Am. Chem. SOC.,1989 111 3225. 62 I. her and H. Alper J. Am. Chem. SOC.,1989 111 927. 63 G. A. Molander and C. Kenny J. Am. Chem. Soc. 1989 111 8236. 64 E. Leonard E. Dufiach and J. Perichon J. Chem. Soc. Chem. Commun. 1989,276. 65 T. Irnarnoto N. Takiyarna K. Nakarnura T. Hatajirna and Y. Karniya J. Am. Chem. SOC.,1989 111 4392. 66 H. Okawa T. Katsuki M. Nakarnura N. Kurnagoui Y. Shuin T. Shinrnyozu and S. Kida J. Chem. Soc. Chem. Commun. 1989 139. 67 D. F. Mullica G. A. Wilson and C. K. C. Lok Znorg. Chim. Acra 1989 163 139. 68 D. F. Mullica G. A. Wilson and C.K. C. Lok Znorg. Chim. Acta 1989 156 159. Sc Y the Lanthanides and the Actinides 85 spectra of single crystals of Na3[Ho(dpa)3]~NaC104~10H,0 (dpaH2 = pyridine-2,6-dicarboxylic acid) have been studied and f-f transition probabilities assigned on the basis of Judd-Ofelt theory.69 A comparison with the results of solution studies indicates that the mechanism of the only hypersensitive transition is vibronic. A number of n.m.r. studies of solution species have appeared. The pseudo contact shifts of the 31P and 170 nuclei in [Ln(PPP),(H20)J7- (PPPH5 = P3010H5 tri- phosphoric acid) have opposite signs indicating that the coordinated water occupies an axial site in s~lution.~’ Accordingly the PPP ligand occupies the equatorial region. The exchange of various P-diketonate ligands between Eu(P-diketonate) and free P-diketonate has been studied by ‘H n.m.r.and I9F n.m.r. spectro~copy.~~ 139La n.m.r. has been used to study the complex formed from LaCl and 18-crown-6 in MeOH.72 The results provide evidence that a C1 ion is present in the first coordination sphere. The n.m.r. data give an equilibrium constant value for complex formation which is in good agreement with previous determinations. Variable pressure 139La n.m.r. studies of La3+ complexation by 4-hydroxypyridine-2,6-dicarboxylicacid (H’dcp) have also been carried out.73 These indicate that chelation is the rate determining step in complex formation following a rapid ion-pair forming pre- equilibrium. A study of the e.s.r. and magnetic properties of Dy(hfac),( NITPh)2 (hfacH = hexafluoroacetylacetone; NITPh = 2-R-4,4,5,5-tetraphenyl-4,5-dihydro-1H-imidazoyl-1-oxyl-3-oxide indicates that coupling between the spins of metal ion and the nitronyl radical is occurring.74 Some studies of lanthanide ions in aqueous solution have appeared.The water exchange rate in octa-aqualanthanide ions from Tb3+to Tm3+ has been studied by 17 0 n.m.r. at pressures up to 250 MPa.75 A similar interchange associative mechanism was found for all the ions and the importance of steric crowding in determining water and Me,NCHO exchange rates was considered. The hydrolysis of Nd3+ in 3 mol dmP3 LiC104 at 60 “C has been studied.76 In order to explain the results at low concentrations (<0.3 mol dmP3 Nd3+) the species Nd(OH)’+ Nd2(OH)2+ and Nd,(OH)tz were proposed while at higher concentrations the latter is replaced by Nd6(0H)ko+.Potentiometric studies indicate that the hydrolysis of Pr3+ in LiC104 solution leads to Pr(OH)2+ Pr,(OH)’+ Pr2(OH)i+ and Pr,(OH):+ .77 The AKUFVE-LISOL system comprising a mixer centrifuge constantly circulating sol- vent and aqueous phases through a scintillation based analytical system provides a means of measuring partition coefficients in continuous solvent extraction processes. This apparatus has recently been used to study the extraction of Tb3+, Ho3+ and Lu3+ from 1 mole dm-’ aqueous (Na,H)C10 by acetylacetone in benzene.78 Radio- chemical methods have also been used to determine the distribution of 15,Gd ions between (BuO),PO and aqueous phosphate solutions providing formation constant 6Y A.Mondry Znorg. Chim. Acta 1989 162 131. 70 J. A. Peters A. Sinnema A. P. G. Kieboom and H. Bekkum Inorg. Chim. Acra 1989 160 7. ” V. Ya Kavum I. V. Kalinovskaya and V. E. Karasev Russ.X Inorg. Chem. 1989 34 951. 72 2. Chen H. Dettman and C. Detsellier Pol-vhedron 1989 8 2029. Y. Ducommun L. Helm G. Laurenczy and A. E. Merbach Inorg. Chim. Acta 1989 158 3. C. Benelli A. Coneschi D. Gatteschi 0.Guillou L. Pardi and P. Rey Znorg. Chim. Acra 1989 160,.1. 73 74 75 C. Cossy L. Helm and A. E. Merbach Inorg. Chem. 1989 28 2699. 76 L. Ciavatta R. Porto and E. Vasca Polyhedron 1989 8 2701. 77 L. Ciavatta R. Porto and E. Vasca Polyhedron 1989 8 983. 78 Y. Albinsson Acta Chem.Scand. 1989 43 919. 86 C.J. Jones data for Gd-phosphate complexes.79 On the basis of the results obtained the use of phosphate buffers in the study of trivalent actinide or lanthanide hydrolysis is deemed inadvisable. Ion exchange studies have provided evidence for complex formation between Eu"' and A,Ph or SbPh in benzonitrite solution.'' In contrast to the order found with high oxidation state d-block metal ions SbPh forms a stronger complex with Eu"' than does AsPh,. Measurements relating to the selectivity of crown ethers and cryptands for lan- thanide ions continue to appear. The macrocyclic effect in lanthanide complexes with 12- 15 18- and 21-membered crown ethers has been studied in propylene carbonate by stability constant measurements for the crown complexes and for the corresponding linear polyethers.81 The linear polyethers form less stable complexes than the macrocyclic ligands and no 1:2 stoichiometry complexes could be identified with the linear ligands.The colorimetric complexant 2-(2-thiazolylazo)-4-methyl-phenol has been used in a study of lanthanide complexation by 18-cr0wn-6.~~ The stability constants of the lanthanide 18-crown-6 complexes were found to decrease with increasing lanthanide atomic number. The stabilities of the 2.2.2 2.2.1 and 2.1.1 cryptate complexes of Ln'" (Ln = Eu Sm Yb) have been compared wth those of the corresponding complexes of the monocyclic ligand 1 ,lo-diaza- 18-cr0wn-6.~~ The cryptands show little selectivity among the oxidation state (III) ions but electrochemical studies reveal some selectivity among the oxidation state (11) lan-thanides.The rate of dissociation of [2.2.1]-cryptand ([2.2.1] = 4,7,13,16,21-penta oxa-l,l0-diazobicyclo-[ 8.8.51-tricosane) from La[2.2.1]( NO3) has been studied using 'H n.m.r. methods.84 The dissociation obeys first order kinetics over the pH range 1 to 13 but above pH 9 hydrolysis to La[2.2.1](OH) species occurs. Complexes of lanthanide ions with macrocyclic nitrogen containing ligands have also been studied. The 'H n.m.r. spectra of Ln,(OEP) (OEPH2 = octa-ethylporphyrin Ln = Ce Pr Nd Sm Eu) provide evidence for inter-ring steric crowding and limited rotation of the OEP alkyl groups.85 The tribasic penta- dentate 'expanded-porphyrin' ligand (2) has been used to prepare complexes with Gd"' Eu'" and Sm"' which are water stable unlike their porphyrin containing counterparts.86 The stability of the Gd"' complex offers the promise of a new type of compound for use as a contrast agent in Magnetic Resonance Imaging (MRI).Also of relevance to medical applications is a report of the synthesis of the Gd3+ complex of (3 n = n2 = 0; R = H) which offers a model for H,DOTA-protein conjugates [R' = amide linked protein; H,DOTA is (3 n = n2 = 0; R = H R' = OH)] used in MRI." The stability constant of the complex with (3) is some lo4 times lower than that with H,DOTA but the relaxivities at high field are similar. 79 L. S. Bingler and R. H. Byrne Polyhedron 1989 8 1315. 'O G. F. Payne 0. L. Keller J.Halperin and W. L. Wolsey J. Chem. SOC.,Chem. Commun. 1989 50. 81 J. C. G. Biinzli and F. Pilloud Inorg. Chem. 1989 28 2638. '*-E. Ohyoshi and S. Kohata Polyhedron 1989 9 8 1561. 83 I. Marolleau J. P. Gisselbrecht M. Gross F. Amoud-Neu and M. J. Schwing-Weill J. Chem. SOC. Dalton Trans. 1989 367. 84 R. A. Torres and P. A. Baisden Inorg. Chem. 1989 28 2807. 85 J. W. Buchler M. Kihn-Botulinski J. Loffler and M. Wicholas Inorg. Chem. 1989 28 3710. 86 J. L. Sessler T. Muroi and G. Hemmi Inorg. Chem. 1989 28 3390. 87 A. D. Sherry R. D. Brown C. F. G. C. Geroldes S. H. Koenig K. T. Kuan and M. Spiller Inorg. Chern. 1989 28 620. Sc Y the Lanthanides and the Actinides Me Me 90Y is a p-emitter with potential applications in radiotherapy.In a search for therapeutic radiopharmaceutical preparations the binding of Y3+ by differing ring size macrocyclic ligands (3 R = H,R' = OH) has been studied.14 The stability constants for complex formation were found to be log K = 24.9 (n = n2 = 0) 19.6 (n = 1 n2 = 0) and 16.3 (n = n = 1) in 0.1 mol dmP3 NMe4N0 solution^.'^ The reagent (3 n = n2 = 0; R' = OH; R = (CH2),NHC(O)CH,OCH2C5H3N-CH=CH2-2,6) has been linked to B72.3 antibodies and the antibody conjugate is being evaluated as a 90Y3+ carrier for cancer therapy. Luminescence Studies.-In doped 38% PbO-62% Si02 glass the stimulated emission cross sections of the potential laser transitions ('F, 'S2) -'I8 and 'F -.+ '1 in Ho3+ are relatively high.88 This is attributed to the narrow effective line widths produced in the presence of Pb2+ as a network modifier.After excitation to the 4f5d configur- ation of Pr3+ in a Gd202S matrix the ion relaxes rapidly to the 4f2 configuration where 3P0 and 'D2 emission occurs.89 Single crystal absorption and emission spectra have been measured from Sm(AP)J (AP = antipyrine) and Sm(AP),(C10J3 and crystal-field interaction parameters were obtained." Chiral discrimination has been observed in the intermolecular energy-transfer process from a racemic terbium tris-(dipicolinate) complex to a resolved ruthenium tris-( o-phenanthroline) com- plex." A large amplification of the optical activity of the system may be obtained through the induction of optical activity into a large population of excited racemic terbium complexes by a small population of excited ruthenium complexes.The effect of pH of the luminescence of Tb(dpa) (dpaH = pyridine-2,6-dicarboxylic acid) in aqueous media has been in~estigated.~ The tris-ligand formulation is the most emissive and the emission intensity decreases rapidly at pH values below 6. The hydration of Eu"' complexed by dicarboxylic acids has been studied by 8X F. Fermi G. Ingleto C. Aschien and M. Bettinelli Inorg. Chim.Acta 1989 163 123. a9 G. Blasse and A. Meijersink Inorg. Chim. Acta 1989 160 29. 90 M. T. Beny and F. S. Richardson Mol. Phys. 1989 66 703. 91 D. H. Metcalf S. W. Snyder S. Wu G. L. Hilmes J. P. Riehl J. N. Demas and F. S. Richardson J. Am. Chem. Soc. 1989 111 3082. 92 T. K. Trout J. M.Belloma R. A. Faltysek E. J. Parks and F. E. Brinckman Znorg. Chim. Acta 1989 155 13. C. J. Jones luminescence methods.93 The mono-malonate complex has 2.3 fewer water molecules than the free hydrated Eu3+ ion. In the cases of 1 :1 complexes with succinate glutarate and adipate 1.5 molecules of water were displaced. The effects of counter ions M+ on the fluorescence spectra of [Eu(PhC(O)CHC(Me)O),]- have been studied for M = Na K Rb and CS.~,The results are consistent with the larger ions producing a reduction in the symmetry of the anion. The structures of the three triboluminescent complexes piperidinium tetrakis(beneoylacetonoito)europate hexakis(antipyrine)terbium tri-iodide and hexa-aquodichloroterbium chloride are de~cribed.~~ The first and last of these complexes contain eight-coordinate metal ions with tetragonal antiprismatic geometries.The remaining complex contains an octahedrally six-coordinate Tb"'ion. The complexes Ln(cca)X (Ln = Sm Eu Gd Tb Dy; ccaH = coumarine-3-carboxylic acid; X = C1 ClO, NO3) and Ln(cca),X have been s~nthesized.~~ The latter compounds exhibit less luminescence than the former. Although the quantum yield for ligand luminescence increases the quantum yield of metal luminescence decreases as a result of energy transfer. A macrocyclic ligand (4) which incorporates two 2,2'-bipyridyl- 1 ,l'-dioxide units forms a stable COPh Eu"' complex which exhibits fluorescence with a total quantum yield of 0.016 when excited at 294 nm.97 LnCp (Ln = Sm Eu; n = 2,3) exhibit chemiluminescence during oxidation by O2.98 Fluorescence was observed from LnCp in frozen solutions.Room temperature luminescence from solutions of ScCpTCl has also been repor- ted.99 The quantum yield was estimated as 0.01 with an excited state lifetime of 2.0 ps in solution at 298 K. Time resolved fluorescence immunoassay (TRFIA) is an important application of lanthanide fluorescence used in medical diagnostics. In this context it has been found that improved sensitivity is obtained by multiple labelling with a Eu3+ complex in a time resolved heterogeneous immunofluorometric assay of cy -fetoprotein in serum using monoclonal antibodies."' 93 P. P. Barthelemy and G. R. Choppin Inorg. Chem. 1989 28 3354. 94 G. M. Murray L. L. Pesterfield N.A. Stump and G. K. Schweitzer Znorg. Chem. 1989 28 1994. 95 A. L. Rheingold and W. King Inorg. Chem. 1989 28 1715. 96 C. B. Castelloni and 0. Carugo Inorg. Chim. Acta 1989 159 157. 97 M. Pietraszkiewcz S. Poppalardo P. Finocchiaro A. Mamo and J. Karpiuk J. Chem. SOC.,Chem. Commun. 1989 1907. 98 R. G. Bulgakov S. P. Kuleshov V. N. Khandozhko I. P. Beletskaya G.A. Tolstikov and V. P. Kazukov Dokl. Akad. Nauk SSSJ? 1989,304 114. 99 B. W. Pfennig M. E. Thompson and A. B. Bocarsly J. Am. Chem. SOC. 1989 111 8947. 100 E. P. Diamondis R. C. Morton E. Reichstein and M. J. Khosravi Anal. Chern. 1989 61 48. Sc Y the Lanthanides and the Actinides 89 Coordination Compounds.-The order in which topics are covered in this section differs from that used last year.Boron-hydride ligands are considered first followed by monodentate ligands with nitrogen then oxygen donor atoms. Following this complexes of bi- then poly-dentate ligands are described with macrocyclic ligands appearing at the end of the section. Amongst the continuing efforts to place lanthanide coordination chemistry into a more systematic structural framework the concept of a 'steric coordination number' for a ligand has been proposed."' This parameter is derived from the solid angle comprising the Van der Waals spheres of the ligand atoms. Such 'ligand effective radii' have been defined on the basis of bond lengths in 274 structurally characterized complexes of lanthanides in oxidation states (11) and (111) and of actinides in oxidation states (111) and (IV).The steric coordination number concept may be used to assist in the comparison of structures and the prediction of bond lengths. In the synthetic sphere the borohydride complexes Ln(BH4),.4N2H (Ln = La Gd Lu) and Ln( BH4),.4( NH2CH2CH2NH2) have been rep~rted.'~~,'~~ The reactions between B10H14 and liquid ammonia solutions of Ln2+ (Ln = Eu Yb) have been investigated and Yb(p-H)2BloH12(MeCN)6 has been isolated and characterized by an X-ray study.'04 The Yb2+ ion is coordinated to six nitrogen atoms from the MeCN ligands and is described as forming two three-centre two-electron bonds to a B,,H;; ion. Structural studies of several thiocynate complexes exhibiting different lanthanide ion coordination numbers have been described.The complexes [Et,N],-[Ln(NCS)6]'SOl (Ln = Er Or Yb SO1 = C6H6 C~HSF C,H,Me Or c6H~Cl) have been prepared and are isomorphous containing six-coordinate lanthanide ions.'05 The [Yb(NCS),I3- ion contains an octahedral Yb3+ ion bound to the N-atoms of the linear NCS-ligands. The two seven-coordinate complexes [Me,N],_ [Ln(NCS)7]-C6H6 (Ln = La Pr) are also isomorphous and in [La(NCS),I4- the La3+ ion is bound to the nitrogen atoms of the NCS- ligands to give a mono-capped trigonal prismatic geometry.'06 The three complexes [Me,N],[ Ln( NCS),] (Ln = Dy Er Yb) are also isostructural and contain seven-coordinate metal ions bound to the nitrogen atoms of the NCS- ligands to give a distorted pentagonal bipyramidal geometry.lo7 The eight-coordinate complexes Et4N[Ln( NCS),( H20)4] (Ln = Nd Eu) are again isomorphous and crystals of the neodymium complex contain Nd3+ ions with a square antiprismatic coordination geometry."' Two of the four N-bonded NCS- ligands occupy mutually cis positions on one square face and the remaining two occupy mutually trans positions on the other square face water-oxygens complete eight-coordination around the Nd3+ ion.Eight-coordinate lanthanide complexes containing six NCS- ligands have also been obtained. Thus the complexes [Me,N],[Ln(NCS),(MeOH)(H,O)] (Ln = La Ce Pr Nd Sm Eu Gd Tb Dy 101 J. Marcalo and A. Pires Polyhedron 1989 8 243. 102 A. Kurbonbekov T. Kh. Alikhanova and U. Mirsaidov Russ.J. Znorg. Chem. 1989 34 347. LO3 A. Kurbonbekov T. Kh. Alikhanova U.Mirsaidov and U. I. Budnikova Russ. J. Inorg. Chem. 1989 34 624. 104 J. P. White 111 H. B. Peng and S. G. Shore J. Am. Chem. SOC.,1989 111 8946. 105 H. Arai Y. Suzuki N. Matsumura T. Takeuchi and A. Ouchi Bull. Chem. SOC.Jpn. 1989 62 2530. 106 F. Matsumoto T. Takewchi and A. Ouchi Bull. Chem. SOC.Jpn. 1989 62 2078. 107 F. Matsumoto N. Matsumura and A. Ouchi Bull. Chem. SOC.Jpn. 1989 62 1809. 108 A. Ouchi Bull. Chem. SOC.Jpn. 1989 62 2431. 90 C. J. Jones Er) are isostructural and contain lanthanide ions bound to six nitrogen atoms from the NCS- ligands and two oxygen atoms from the MeOH and H20 ligands to give a square antiprismatic geometry.'" The lanthanide amide complexes Ln[N(SiMe3),],Cl(t.h.f.) (Ln = Eu Gd or Yb) and Y[N(SiMe,),)]Cl(t.h.f.) have been prepared from LnC13 or YCl and Li[N(SiMe,),]."' Structural studies of the Gd and Yb complexes confirm the presence of dimeric Ln(p-Cl,)Ln cores in these complexes.The lanthanide ions are in an approximately trigonal bipyramidal coordination environment with one bridg- ing C1- and the oxygen of the t.h.f. occupying the axial sites. The remaining bridging C1- and two N(SiMe,) ligands occupy the equatorial sites. The reactions between LnCl and Napz (pzH = pyrazole) or NaMe2pz(Me2pzH = 3,5-dimethylpyrazole) afford polymetallic products of general formula Ln3( p -Me,pz) (q2-Me2pz),(p3-0)-Na,(L) (Ln = Y Ho Yb Lu and L = t.h.f.; or Ln = Y Ho Yb and L = Me,pzH)."O X-Ray diffraction studies of two complexes (Ln = Yb with L = t.h.f.and Ln = Ho with L = Me,pzH) reveal similar structures in which an oxygen atom lies at the centre of a trigonal bipyramid comprising three equatorial lanthanide ions bound to the oxygen and two apical sodium ions linked to the lanthanide by bridging pyrazolide ligands. Each sodium ion is also bound to either a t.h.f or a Me,pzH ligand and each lanthanide ion is also bound to an q2-Me2pz- ligand. Two reports of structural studies on compounds containing pnicnogen oxide ligands have appeared. The X-ray crystal structure of Eu( NO3),( Ph3AsO),-4H20 reveals the presence of three bidentate nitrate ligands along with the three Ph,AsO ligands giving a coordination number of nine for the Eu3+ ion. The coordination geometry may be described as distorted octahedral if the nitrate ions are presumed to occupy single coordination sites."' The Ph,AsO ligands then occupy mutually meridional positions in the octahedron.A series of phosphine oxide complexes [Ln(Ph3PO)5C1][FeC1,] (Ln = La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er and Y) has also been prepared.Il2 An X-ray study of the complex with Ln = La reveals a distorted octahedral geometry about the six-coordinate La3+ ion. The polymeric heterobimetallic mixed lanthanide-mercury complexes {[Hg2-LnL,(NO,),]} (Ln = La to Gd; L = C4H6N0 derived from 2-pyrrolidone) and (Ln = Y and Tb to Yb) have been ~ynthesized."~ {[Hg3Ln2L6(N03)6]n} The struc- tures of the complexes with Ln = Eu and Tb were determined. They contain nine-coordinate lanthanide ions in an essentially tricapped trigonal prismatic coordi- nation environment.The complete structures consist of polymeric chains cross linked by nitrate ligands and partial structures showing the chains are illustrated in Figure 3. The zero-field splitting parameters D and A were obtained from e.p.r. measure- ments. Among the compounds containing purely inorganic ligands the double lanthanum barium perxenate complex La2Ba( Xe0,),.3H20.Na2CO3 has been 109 H. C. Aspinall D. C. Bradley M. B. Hursthouse K. D. Sales N. P. C. Walker and B. Hussain J. Chem. SOC.,Dalton Trans. 1989 623. 'lo H. Schumann P. R. Lee and J. Loebel Angew. Chem. In?. Ed. Engl. 1989 28 1033. 'I1 U. Casellato R. Graziani U. Russo and B. Zarli Znorg. Chim. Acta 1989 166 9. 112 H. K. Wang M. J. Zhong X.Y. Jing J. T. Wang R. J. Wang and W. G. Wang Znorg. Chim. Acta 1989 163 19. D. M. L. Goodgme D. J. Williams and R. E. P. Winpenny J. Chem. SOC.,Dalton Trans. 1989 1439. Sc Y the Lanthanides and the Actinides ,--1. Figure 3 (a) A partial structure showing the polymer chain in [EuHg,( C4 JO),(NO3)31 with the nitrate groups omitted for clarity; (b) A partial structureshowing the polymer chain in [Tb,Hg,(C,H,No),(No,),]" with the nitrate groups omitted for clarity (Reproduced by permission from J. Chem. SOC.,Dalton Trans. 1989 1439) reported along with the preparation of La4(Xe06)3-3H20. Na2C03.'I4 A structural study has shown that the hydroxide complex Nd2(0H),(C104)2~5H20 contains eight-coordinate Nd3+ ions in an irregular coordination geometry and linked via bridging ClO ligand~."~ There has been increased interest in lanthanide alkoxide complexes and a number of papers have appeared on this topic.This is partly as a result of the search for molecular species which might form the basis of new synthetic routes to ceramic superconductors or which may be useful in other fabrication processes such as MOCVD. The direct synthesis of yttrium alkoxides from the metal and alcohols has led to polymetallic yttrium alkoxide complexes two of which have been structurally chrac- terized. The reaction between yttrium metal and 2-propanol affords Y,O(OPr'), which has been characterized by 'H I3C and ''Y n.m.r. spectroscopy."6 Crystals of the complex contain a square pyramidal Y5cluster containing a basal p,-oxygen 114 L.D. Shuslov N. S. Tokmacheva Sh. Sh. Nabiev E. K. Il'in V. D. Kilimov and V. P. Ushakov Russ. J. Znorg. Chem. 1989 34 946. 115 I. Csoregh E. Huskowska A. Ertan J. Legendzicwicz and P. Kierkegaard Acta Chem. Scand. 1989 43 829. 116 0.Poncelet W. J. Sartain L. G. Hubert-Pfalzgraf K. Folting and K. G. Caulton Znorg. Chem. 1989 28 263. C.J. Jones 012 011 Figure 4 The Y,O1 substrucrure in Y,O(OPr'), (Reproduced by permission from Inorg. Chem. 1989 28 263) as illustrated in Figure 4. In addition to the five terminal OPr' ligands there are four p3-OPr' ligands capping triangular faces and four p2-OPri ligands bridging the edges of the square base. Yttrium turnings also react directly with 2-methoxyethanol in toluene to give [Y(OC2H40Me)3]lo which contains a cyclic array of ten yttrium centres as shown in Figure 5.Il7 This compound can also be prepared by alcoholysis of Y,O(OPr'), .Atempts to synthesize Y(OBu') have failed because of heterolytic C-0 cleavage reactions leading to yttrium oxides.l18 However the more robust Si-0 bond in 0-SiPh3 allows [Y(OSiPh,),(t.h.f.),]-t.h.f.to be isolated. This complex contains three t.h.f. ligands in a mutuallyfac arrangement to give a distorted octahedral geometry about six-coordinate Y3+. The large Y -0-Si angles [average 171( l)"] and short Y-OSi distances [2.12(2) A] were taken to indicate extensive Y-O(Si) multiple bonding in the compound. A series of cerium alkoxides Ce(OBu'),(NO,)b(solvent),Nad(a = 1 to 6; b = 0 to 3; c = 2 4; d = 0 2; a + b = 4 + d) have been identified along with Ce2(OBu'),Na and Ce3(OBu')lo0.'19 In C~(OBU')~(NO~)~(HOBU')~ the Ce4+ ion is eight-coordinate and the coordination geometry may be described as distorted octahedral if the two trans bidentate nitrates are each considered to occupy one coordinate site.In Ce(OBu'),( ~-OBU')~(~~-OBU')~N~ the Na+ ion is coordinated to two terminal and the two bridging alkoxides of the binuclear cerium complex as illustrated in Figure 6. In the complex Ce(OBu'),( ~-OBU')~( ~~-0Bu')~Na~-(MeOCH2CH20Me)2 the Ce4+ ion is in a six-coordinate distorted octahedral en- vironment with Na' ions capping two O3 faces as shown in Figure 7. The thermal decomposition of Ce(OCBu\) affords [Ce(OCHBu\)J2 (90%)from isobutene elimi- nation and [Ce(OCHBu',),H] (10%) from Bu',CO elimination.'20 The structure of [Ce(OCHBu;),] contains two pseudo-tetrahedral Ce3+ ions each carrying two terminal OCHBub ligands and linked via two p2-OCHBu' ligands.The Ce202 moiety is planar with 0-Ce-0 = 74.3(1)' and Ce-0-Ce = 105.7(1)". Ce(OSiPh,),.x(MeOCH,CH20Me) (0.5 < x < 1.0) has been prepared and 117 0. Poncelet L. G. Hubert-Halzgraf J. C. Doran and R. Astier J. Chem. Soc. Chem. Commun. 1989 1846. 118 M. J. McGeary P. S. Coan K. Folting W. E. Streib and K. G. Caulton Znorg. Chem. 1989 28 3283. 119 W. J. Evans T. J. Derning J. M. Olofson and J. W. Ziller Znorg. Chern. 1989 28 4027. I20 H. A. Stecher A. Sen and A. L. Rheingold Inorg. Chem. 1989 28 3282. Sc Y the Lanthanides and the Actinides Figure 5 The structure of [Y(OC2H,0Me),], (Reproduced by permission from J.Chem. Soc. Chem. Commun. 1989 1846) Figure 6 The structure of Ce(OBu'),(p-OBu'),(p3-OBu'),Na (Reproduced by permission from Inorg. Chem. 1989 28 4027) C. J. Jones C c34 Figure 7 The structure of C~(OBU'),(~-OBU')~( p3-OBu'),Na2( MeOCH,CH,OMe) (Reproduced by permission from Inorg. Chem. 1989 28 4027) structurally characterized.121 The Ce4+ ion exhibits a distorted octahedral six-coordi- nation geometry with short Ce-O(Si) bond lengths [2.098( 10)-2.133(10) A] and longer Ce-O(C) bond lengths [2.575(10) and 2.587(10) A]. In addition to work on alkoxide complexes some results using aryloxo ligands have also been reported.The sterically demanding ligand 2,6-dimethylphenoxide (ArO-) has been used to prepare halide- and oxide-free Y3+ complexes.'22 The complex Y(OAr),(t.h.f.) contains Y3' in a distorted octahedral geometry with a mutually fac arrangement for the OAr ligands. The complex [Y(p-0Ar)-(OAr)2(t.h.f.)]2 was also obtained and contains five-coordinate Y3+ centres linked by bridging phenoxide oxygens. In this case the coordination geometry at Y is distorted square pyramidal. Some general methods for the preparation of monomeric Yb2+aryloxide complexes have been de~cribed.'~~ These involve reactions between Yb and TlOAr' (Ar' = C,H2Bu:-2,6-Me-4) or Yb{N(SiMe3)2}2(OEt2)2 and Ar'OH. The complex Yb(OAr'),( t.h.f.) has an unprecedented square pyramidal stereo- chemistry around Yb2 whereas Yb(OAr'),(Sol) (Sol = t.h.f.or OEt2) have approxi- mately tetrahedral geometries. A calixarene complex of Eu3+ has been ~ep0rted.l~~ This was obtained from the reaction between Eu3+ ions and p-tertiarybutylcalix-[4]-arene (H,L) to give [Eu2( HL),(dmf),].7 dmf (dmf = N,N-dimethylformamide) which contains two Eu3+ centres bridged by one phenoxy oxygen from each of two calixarene ligands as shown in Figure 8. The X-ray crystal structure of Ce( NO3),( MeOCH2CH20Me)2 has been deter- mined and the molecule found to contain a ten-coordinate Ce3+ ion bound to three 121 P. S. Gradeff K. Yunlu A. Gleizes and J. Galy Polyhedron 1989 8 1001. 122 W. J. Evans J. M. Olofson and J. W. Ziller Inorg. Chem. 1989 28 4308. 123 G.B. Deacon P. B. Hitchcock S. A. Holmes M. F. Lappert P. MacKinnon and R. H. Newnham J. Chem. SOC.,Chem. Commun. 1989 935. 124 B. M. Furphy J. M. Harrofield M. I. Ogden B. W. Skelton A. H. White and F. R. Wilner J. Chem. SOC.,Dalton Trans. 1989 2217. Sc Y the Lanthanides and the Actinides Figure 8 The structural arrangement of the dimeric calixarene complex [Eu(p-tertiarybutylcalix-[4]-arene)(d.m.f.),12 (Reproduced by permission from J. Chem. Soc. Dalton Trans. 1989 2217) bidentate nitrate and two bidentate dimethoxyethane ligand~.'~' The five bidentate ligands form an approximately trigonal bipyramidal array around the cerium. Isomorphic crystals of the Dy3+ and Ho3+ proline complexes [Ln(C5H9N02)2(H20)5]C13 (Ln = Dy Ho) have been prepared.The holmium com- plex contains eight-coordinate Ho3+ ions in a distorted bicapped trigonal-prismatic geometry.'26 The carboxylate groups in the proline ligands act as bridging groups linking the Ho3+ ions in polymeric chains. The effect of structural features on the hypersensitive f-f transitions of these compounds was evaluated. Several papers refer to P-diketonate complexes of the lanthanides. Studies of the mass spectral fragmentation patterns of the complexes Ln(acac) (acacH = pentane-2,4-dione) provide evidence that the complexes containing Sm Eu and Yb undergo an oxidation state change from Ln'" to Ln".'27 Complexes con- taining Ce or Gd do not exhibit this behaviour and the Ln3+ oxidation state is preserved. The crystal structure of Gd[CF,C(O)CHC(CF,)O],L (L = 2-ethyl-4,4,5,5-tetramethyl-4,5-dihydro- 1H-imidazolyl-1-0xy1-3-oxide) reveals that linear chains of Gd[CF,C(O)CHC(CF,)O] moieties linked by bridging nitroxide radicals are present.'28 Several models are described which account for the anti- ferromagnetic coupling observed in this compound.The molecular structure of 125 P. S. Gradeff K. Yunlu T. J. Deming J. M. Olofson J. W. Ziller and W. J. Evans Inorg. Chem. 1989 28 2600. 126 J. Legendziewicz T. Gtowiak E. Huskowska and D. Cong-Ngoan Polyhedron 1989 8 2139. 127 S. Lis A. S. Ptaziak and M. Elbanowski Inorg. Chim. Acta 1989 155 259. 128 C. Benelli A. Caneschi D. Gatteschi L. Pardi and P. Rey Inorg. Chem. 1989 28 275. C. J. Jones [Nd4(p3-OH)2(p2 pl-acac)6(acac)4] reveals two dinuclear Nd,(OH)(acac) units linked by two triply bridging pyramidal p-OH ligands and by two bridging-chelating acac ligand~.',~ The metal atoms are eight-coordinate with a distorted square- antiprismatic geometry as illustrated in Figure 9.The bifunctional ligands (Pr'O),P(=O)CH,S(=O),,R (R = C6Hll or C6H4Me-4 and n = 2; R = C6H4Me-4 and n = 1) and Ph,P(=0)CH2S(=0),NMe2 have been prepared and their com- plexation reactions with La( NO3) and Gd( NO3) in~estigated.'~' In the latter case Gd( NO,),[ Pri(O),P(O)CH,S(O)(C,H,Me-4)]~H2O was isolated and a structural study carried out. This revealed that the Gd3+ ion is nine-coordinate and bound to three bidentate nitrate groups ,a water molecule and the bifunctional ligand bound in a bidentate manner by the phosphoryl and sulphinyl oxygens.n Figure 9 The structure of Nd4(p-OH)2(p2,p,-acac),(acac) (Reproduced by permission from Polyhedron 1989 8 2183) A number of heteroleptic hydro-trispyrazol- 1-ylborate complexes of the lan- thanides have been described and some examples structurally characterized. The air and moisture stable complexes Ln(HBpz,),(acac) (Ln = La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Yb Tm Lu and Y) have been prepared.131 Structural studies show that the lanthanide ions are eight coordinate and that the compound with Ln = Ce has an essentially bicapped trigonal prismatic coordination geometry as shown in Figure 10 while that with Ln = Yb has a structure more in accord with a square antiprismatic structure as shown in Figure 11.'H n.m.r. data show that intramolecular ligand reorganization occurs in solution. The heteroleptic tropolonate complexes L~(HBPZ,)~(O,C,H~) (Ln = La Ce Pr Nd Sm Eu Tb Yb Lu Y) 129 0. Poncelet and L. G. Hubert-Pfalzgraf Polyhedron 1989 8 2183. S. Karthikeyan R. R. Ryan and R. T. Paine Znorg. Chem. 1989 28 2783. M. A. J. Moss C. J. Jones and A. J. Edwards J. Chem. SOC.,Dalton Trans. 1989 1393. 130 131 Sc Y the Lanthanides and the Actinides Figure 10 The structure of Ce(HBpz,),(acac) (Reproduced by permission from J. ,Chem. SOC. Dalton Trans. 1989 1393) Figure 11 The structure of Yb(HBpz,),(acac) (Reproduced by permission from J. Chem. Soc. Dalton Trans. 1989 1393) have also been prepared and the molecular structure of the Yb complex deter- mined.'32 The Yb3+ ion is eight-coordinate with a distorted square antiprismatic geometry.The complexes are all air and moisture stable but those containing La Ce and Pr are insoluble in CH2C12. The binuclear heteroleptic oxalate complexes 13' M.A. J. Moss and C. J. Jones Polyhedron 1989 8 117. 98 C. J. Jones [{L~(HB~Z~)~]~(C~O,) Mass (Ln = Y Sm Dy Yb or Lu) have been ~ynthesized.',~ spectral data support the binuclear formulation while 'H n.m.r. data are consistent with the binding of the bridging oxalate to form a five-membered chelate ring as was the case for the tropolonate complexes. Continuing this series to incorporate bidentate monoanionic ligands with smaller 'bite angles' the heteroleptic carboxylate complexes Ln{HBpz,},(O,CR) (Ln = Y Sm Eu Yb Lu and R = Ph; Ln = Y Yb Lu and R = Me) were prepared.', Yb[Hbpz3I2(O2CPh) is monomeric in the solid state containing an eight-coordinate Yb3+centre with a coordination geometry which lies on the geometric pathway from square antiprismatic to dodecahedral.The hexanuclear mixed metal copper-lanthanide complexes Cu,Ln2L8-(LH)4(OH)2(N03)4(Hz0)2 (Ln = Dy or Gd; LH = 2-(1H)-pyridone C5H,NO) have been prepared and their solid state structures determined.',' The lanthanide ions are nine-coordinate with a coordination geometry approximating to face-capped square-antiprismatic. The copper ions occupy two different sites both being five- coordinate. The 2-pyridone ligand is trinucleating with the oxygen bound to lan- thanide and one copper ion and the nitrogen bound to a second copper ion.A number of papers have been concerned with the use of amino acids or their derivatives as ligands for lanthanide ions. The crystal structures and fluorescence spectra of Ln2(~-Glu)2(C104)4-9Hz0 (L-Glu = glutamate; Ln = Nd Eu Dy Ho) have been investigated and the absorption spectra analysed on the basis of Judd-Ofelt Crystals of Ho( ~-Asp)C1,-6H,0 (L-As~= aspartate) contain eight-coor- dinate Ho3+ ions bound to five H20 molecules and three carbonyl oxygens from different bridging L-As~ ligands.',' o-Hydroxyacetophenone-(N-benzoy1)gly-cinehydrazone (abzgH,) forms the complexes [Ln(ab~gH~)C1~(H~0)~]ClLa, (Ln = Pr Nd Sm and Eu) and Ln(abzg)(OH)(H,O) in which the ligand is proposed to be neutral and bidentate or dianionic and tridentate re~pectively.'~~ The complexes [Ln(b~gH)~[C1~(0H,)-nH~0 (Ln = La Pr Nd Sm Eu Gd Tb Dy or Y n = 1 or 2 and bzgH = N-benzoylglycine hydrazide) have been re~0rted.l~~ The ligand bzgH is thought to be bidentate in all the complexes.Other polydentate ligand complexes which have been reported include [Ln(Hapfh),Cl]Cl (Ln = La Pr Nd Sm Eu Gd and Dy; Hapfh = 2-acetylpyridine-2'-furoylhydrazone, 2-OC4H,C( =O)NHN=C( Me)C5H4N-2') and Ln(apfh),(OH).'40 Infra red studies indicate that in both cases the ligand is bound in a tridentate manner. Potentiometric spectroscopic and t.g.a. data have been reported for trivalent lanthanide complexes of 1,5-bis(o-carboxyphenyl)-3-acetyl and formazan (o-H0,CC6H,N=N-C(COMe)=NNH-C6H4-o-Co2H) 1-(0-carboxypheny1)-5-(o-hydroxyphenyl)-3-acetyl formazan (o-H02CC6H4N=N-C(COMe)=NNHC6H4-o-OH).'41Ferrocene has appeared as a component of ligand 133 M.A. J. Moss and C. J. Jones Polyhedron 1989 8 2367. 134 M. A. J. Moss and C. J. Jones Polyhedron 1989 8 555. 135 D. M. L. Goodgame D. J. Williams and R. E. P. Winpenny Polyhedron 1989 8 1531. 136 I. Csoregh M. Czugler P. Kierkegaard J. Legendzicwicz and E. Huskowska Acfa Chem. Scand. 1989 43 735. 137 I. Csoregh P. Kierkegaard J. Legendzicwicz and E. Huskowska Acta Chem. Scand. 1989,43 636. 138 T. R. Rao and G. Singh Transition Met. Chem. 1989 14 471. 139 T. R. Rao G. Singh and I. A. Khan Transition Met. Chem. 1989 14 15. 140 B. Singh and P.K. Singh Transition Met. Chem. 1989 14 411. 141 S. S. Badawy Y. M. Issa and H. M. Abdel-Fattah Transition Met. Chem. 1989 14 401. Sc Y the Lanthanides and the Actinides systems for lanthanide ions. Formylferrocene benzoylhydrazone (CpFeCq5-C5H4CH=NNHC(0)Ph = LH) forms complexes of formula LnL,-nH,O (Ln = Y or a lanthanide element) in which the ligand binds in the deprotonated enolate form.142 The binding of alkaline earth and lanthanide ions to the ferrocenyl contain- ing cryptand (5) has been studied by electro~hemistry.'~~ The binding an electron Fe transfer processes are summarized in Scheme 1. A linear correlation was found between LnK and the radius :charge ratio of the bound cation. Pyridinaldazine (paa) and pyrrolaldazine (pyaaH,) complexes of lanthanide ions have been described.14 [Ln(L)Cl,(H20),]C1~rnH20 (Ln = Ce Nd Sm Yb; L = paa or pyaaH, n = 2,4,rn = 0 1,2,3.5) were prepared from LnC13.The reaction between YbC13.6H20 and pyaaH afforded Yb,(pyaa)Cl,( H20)4.2H20. (5) + M"+ K [(5):M"+] (f) = free cryptand potential (c) = cryptate redox potential Scheme 1 The first structural study of a lanthanide complex with a tetradentate ligand has appeared.'45 The crystal structure of [C5H,,NH2][Er(sa12en)2] (sal,enH = N,N'-ethylenebissalicylaldimine) shows that the metal ion is eight-coordinate with a distorted square antiprismatic geometry. The sa1,en ligands are coordinated in part to both square faces as illustrated schematically in Figure 12. The structures of Ca[ Er(egta)(OH,)],.12H,0.Me2C0 (egtaH = 3,12-bis(carboxymethyl)-6,9-dioxa-3,12-diazatetradecanedioicacid) and Ca[ Nd(egta)( OH2)I29H20 have also been determined.'46 The former complex contains nine-coordinate erbium while the latter contains ten-coordinate neodymium. There has been increasing interest in complexes of the lanthanides with macro- cyclic ligands and a number of new compounds of this type have been reported. 142 M. Yongxiang M. Zhongqian Z. Gang M. Yun and Y. Min Polyhedron 1989 8 2105. 143 C. D. Hall N. W. Sharpe I. P. Danks and Y. P. Sang J. Chem. SOC.,Chem. Commun. 1989 419. 144 M. M. Dawod F. I. Khalili and A. F. Seyam Polyhedron 1989 8 21. 145 S. Mangani A. Takeuchi S. Yamada and P. Orioli Inorg. Chim. Acta 1989 155 149.146 C. K. Shaver and 0.P. Anderson J. Chem. SOC.,Dalton Trans. 1989 185. 100 C. J. Jones Figure 12 A schematic diagram of the coordination environment of the Er3+ ion in (C H1oN H2)Ed42en 2 The complexes LII(NCS)~L[Ln = Y or Eu L = (6) R = Me] contain two kinds of nine-coordinate molecule with different macrocycle conformations as shown in Figure 13.14' Yttrium ions can be used in the template synthesis of the N4macrocycle (7) from 2,6-diacetylpyridine and hydrazine to give [Y(7)( N03)3]-2H20.'48 Varying the reaction conditions can lead to the formation of the open chain ligands (8) and (9) found in the complexes [Y(8)(H20)2]C13.2H20 and [Y(9)(N03),].2H20 and [Y(9)2]C1,.[Y(9),]Cl3.2H2O. A structural study of the yttrium complex of (6) (R = Me) [Y(C22H26N6)(02CMe)2H200.5]C104 reveals two different structures in Me &Me N N \ Me Me (6) R = H Me (7) Me &Me N 0 \ Me 147 G.Bombieri F. Benetollo A. Polo L. deCola W. T. Hawkins and L. M. Vallarino Polyhedron 1989 8 2157. 148 W. Radecko-Paryzek Polyhedron 1989 8 1217. Sc Y the Lanthanides and the Actinides C(1011 Figure 13 The two diflerent macrocycle conformations found in Eu"' (NCS) . (Reproduced by permission from Polyhedron 1989 8 2157) the crystal 1atti~e.l~~ The metal is nine-coordinate with a coordination geometry best described as a monocapped square antiprism. Yttrium acetate is effective in stimulat- ing the template synthesis of the macrocyclic ligand (6) from 1,2-diarninoethane and the dicarbonyl substituted pyridine precursor.A series of bis-porphyrin complexes of Ce4+ has been prepared from cerium acetylacetonate complexes and tetraphenylporphyrin or tetra-p-chlorophenylp~rphyrin.~~~ In the case of hexadecahydrotetrabenzorphyrin a bis-cerium (111) 'triple-decker' complex is also found. The crystal structure of Ce(OEP)(TPP) (OEPH2 = octaethylporphyrin L 49 G. Bombieri F. Benetollo W. T. Hawkins A. Polo and L. M. Vallarino Polyhedron 1989 8 1923. I50 J. W. Buchler A. D. Cian J. Fischer P. Hamrnerschmitt J. Loffler B. Scharbert and R. Weiss Chern. Ber. 1989 122 2219. 102 C. J. Jones TPPH2 = tetraphenylporphyrin) reveals a staggered conformation for the two por- phyrin ligands giving a square antiprismatic coordination geometry for Ce4+.The Eu and Gd complexes of the macrocyclic Schiff base (6) (R = Me) have been prepared and the complex Gd(6)(02CMe)2Cl.4H20 characterized by X-ray crystal- 10graphy.I~ The Gd3+ ion is ten-coordinate being bound to the six nitrogen atoms of the macrocycle and to two bidentate acetate ligands. The complex exhibits a relaxivity in aqueous solution comparable with that of the Gd3+ aqua ion and is thus of interest as a potential contrast agent in MRI. The template condensation of f7-n /-N 0 0 NT 2,6-diformyl-p-creso1 with 3,6-dioxa- 1,8-0ctanediamine to give ( 10) may be effected by Ln3+ (Ln = La to Tb).15' The structure of the Gd complex shown in Figure 14 reveals that a homobinuclear complex is formed within the macrocycle.Lumines- cence studies of the Eu complex provided evidence of Eu-Eu interactions. The Pr3+ complex of the hexadentate macrocycle (1 1) have been ~ynthesi2ed.l~~ The crystal Figure 14 The structure of Gd,(lO)(NO,),-H,O (Reproduced by permission from J. Chem. Soc. Chem. Commun. 1989 1531) 151 I. A. Kohwa S. Folkes D. J. Williams S. V. Ley C. A. O'Mahoney and G. L. McPherson J. Chem. Soc. Chem. Cornmun. 1989 1531. 152 F. Benetollo G. Bombieri L. DeCola A. Polo D. L. Smailes and L. M. Vallanno Inorg. Chem. 1989 28,3447. Sc Y the Lanthanides and the Actinides SmCp (t.h.f.) Me Cp (t.h.f.) Sm (11) (12) structure of [Pr( NO,),( MeOH)( 12)]C10,-0.5MeOH~0.5H20 has been determined and reveals a saddle shaped conformation for the ligand with an 11-coordinate P8' ion bound also to methanol and two bidentate nitrate ions.0rganolanthanides.-Once again reports of organolanthanide compounds are domi- nated by complexes containing cyclopentadienide or a derivative of cyclopen- tadienide as a ligand. Attempts have been made to prepare Ce4+ complexes of cyclopentadienide by the reaction of NaCp with (NH4)2[ce(No3)6].125 The reaction involving respective 1:1 equivalents of these reagents results in reduction of Ce4+ to Ce3+ and the 6 1 reaction affords CeCp3(t.h.f.) in high yield. The 5:1 reaction affords thermally unstable CeCp,( NO,),Na( t.h.f.) . More success was achieved by using OBu' as a co-ligand and CeCp,(OBu') may be prepared in high yield from Ce(OBut),( NO,),(t.h.f.) and NaCp.The trinitrate Ce( NO,),(OBu')t.h.f. reacts to give a mixture of CeCp,(OBu') and CeCp3(0Bu').153 The X-ray structure of the latter complex reveals a distorted tetrahedral arrangement of the four ligands around the Ce4+ ion. The tetrakis-cyclopentadienyl anions Na[LnCp,].t.h.f. (Ln = La Nd) Na[ PrCp,] and NaCp.Na[CeCp,].t.h.f. have been prepared.154 Structures based on LnCp,(p,q'-C,H,)Na(t.h.f.) (n = 0,l) are proposed. In the solid state the structure of Yb( q5-C5H4Me) consists of a Yb3+ ion trigonally coordinated to the centroids of three q5-C5H,Me ligands.', Other complexes of monosubstituted cyclopen-tadienide ligands include La( ButC5H4),(t.h.f.) Sm( ButC5H4), [Sm( ButC5H4),C1] [Lu( Bu'C,H~)~C~] and Lu( Bu'C,H4)C1,.2t.h.f.which have been prepared by the reactions between the appropriate lanthanide trichloride and NaBu'C,H4 .156 The 2,4-dimethyl-penta-l,4-dienyl complex Nd(C7HI ,)C12.0.33t.h.f. has also been pre- pared and crystallizes with a hexameric Nd6(C,H,,)&1,,.t.h.f. unit which contains two Nd3C1 units connected by two chloride bridges.'57 The C7H11 ligands are bound in the q5-mode. Synthetic routes to mono-pentamethylcyclopentadienyl-yttrium,-lanthanum and -cerium complexes have been explored.'58 Reaction of LnR (R = hydrocarbyl) 153 W. J. Evans T. J. Deming and J. W. Ziller Organornetallics 1989 8 1581. 154 K. Jacob M. Glanz K. Tittes K. H. Thiels I. Pavlik and A. LyEka Z. Anorg. A&. Chern. 1989 577 145. 155 A. Hammel W. Schwarz and J.Weidlein J. Organomet. Chem. 1989 363 C29. 156 A. L. Wayda J. Organornet. Chem. 1989 361 73. 157 J. Sieler A. Simon K. Peters R. Taube and M. Geitner J. Organornet. Chem. 1989 362 297. 158 M. Booiu N. H. Kiers H. J. Heeres and J. H. Teuben J. Organornet. Chern. 1989 364,79. 104 C.J. Jones with Cp*H generally gave LnCpzR. However YCp*(C6H4CH2NMe2-2)2 was obtained from Y(C6H4CH2NMe2-2),and Cp*H. The heteroleptic cyclopentadienyl- idenyl lanthanide complexes LnCp,Ind (Ln = Sm Dy Ho Er Yb; Ind = C9H7) have been prepared from LnCp,Cl and are less air sensitive than their counterparts LnCp Other heteroleptic complexes have been prepared which contain a steri- cally bulky hydrocarbyl ligand and the X-ray structures of LaCp"[CH(SiMe,),] (Figure 15) and LaCp*[CH( SiMe3)2]2(t.h.f.) have been determined.I6' The former n V Figure 15 The structure of LaCp*[CH(SiMe,),] showing the methyl hydrogens ofthe Me groups associated with the agostic interactions but omitting the other methyl hydrogens for clarity.(Reproducedby permission from Organometallics 1989 8 255) constitutes the first structurally characterized example of a salt-free and solvent-free monocyclopentadienyl lanthanide alkyl complex and is prepared by reaction of the latter complex with Me,SiI. Both complexes contain unusual agostic Si-C bonds which help to stabilize the sterically unsaturated lanthanum ion. Agostic interactions were also found between yttrium and the C-H bonds of the N-CH groups in YCp*( o-C6H4CH2HMe2) .I6' Thermolysis of this compound affords N,N-dimethyl-benzylamine and YCp*[o-C,H4CH2NMe(CH2-~)][~-o-(C6H4CH2NMe(CH2-~)] YCp*(t.h.f.) in which both aryl and N-methylene bridging groups have been formed as shown in Figure 16.The lanthanoid alkyl complexes Ln[CH(SiMe,),],(p-Me)Li(pmdeta) (Ln = La or Sm,pmdeta = N,N N',N",N"-pentamethyl-diethylenetriamine)have been pre- pared.'62 A structural study shows that the samarium complex has approximately tetrahedral coordination environments around Sm and Li with a near linear (174(2)") Sm-Me-Li unit. Alcoholysis of LnCpT[CH(SiMe,),] (Ln = La or Ce) by Bu'OH 159 Z. Zhennan W. Zhongzhik D. Baohu and Y. Zhongwen Polyhedron 1989,8 17. 160 H. van der Heijden C. J. Schaverien and A. G. Orpen Organometallics 1989 8 255.161 M. Booij N. H. Kiers A. Moefsma J. H. Teuben W. J. J. Smeets and A. L. Spek Organometallics 1989 8 2454. 162 P. B. Hitchcock M. F. Lappert and R. G. Smith J. Chem. SOC. Chem. Commun. 1989 369. Sc Y the Lanthanides and the Actinides n Figure 16 The structure of YCp*[o-C,H4CH2NMe(~-CH*)][~-o-C,H,CH,N-CH*)]-YCp*t.h.f. (Reproduced by permission from Organornetallics 1989 8 2454) affords [LnCp*( p2-OBu')(OBu')]2 .163 The X-ray structure of the Ce compound reveals a pseudo-tetrahedral geometry about each Ce atom based on the Cp* ligand a terminal OBu' ligand and two p,-OBu' ligands. The two terminal OBu' ligands are in a cis orientation with respect to the Ce(p-OBu'),Ce unit. The aryloxy derivatives Ce( R)(OAr) (R = Cp* or 1,3-diphenyl-2-methylindene; Ar = 2,6-Bu\C6H3) may be prepared from Ce(OAr) and LiR.'64 The reaction of CeCp*(OAr) with LiCH(SiMe3)2 or NaN(SiMe3)2 affords CeCp*(R')2 [R'= CH(SiMe3) or N(SiMe,),] of which the former is a catalyst for ethene but not propene polymerization.The X-ray structures of CeCp*(R2) (R2 = OAr R') show that in each case the metal is trigonally coordinated to a Cp* ligand and the two ligands R2. A series Of complexes YbCp2(02CR) (R = Me CF3 Ph c6F6 C6Br5 MeO2CC6F4 C6H2Me,-2,4,6 NC5H4-2) have been prepared by oxidation of YbCp,(MeOCH,CH,OMe) with M(02CR) (M = Hg" n = 2 or M = Tl' n = l)? The complexes with R = Me CF3 Ph or C6F5appear to be dimeric. Other heteroleptic complexes containing bidentate uninegative oxygen ligands include LnCp,(sal)3- and LnCp,(fur),- (Ln = Nd Yb; n = 1,2; salH = salicylaldehyde; furH = furfuryl alcohol) have been synthesized and shown to be 163 H.J. Heeres J. H. Teuben and R. D. Rogers J. Organornet. Chern. 1989 364,87. 164 H. J. Heeres A. Meetsma J. H. Teuben and R. D. Rogers Organornetallics 1989 8 2637. 165 G. B. Deacon and D. L. Wilkinson Aust. J. Chem. 1989 42 845. 106 C. J. Jones thermally unstable with respect of disproportionation according to equations (1) and (2) where L = sal or fur.'66 2LnCpL + LnCp,L + LnL (1) 3LnCp,L -+ 2LnCp + LnL (2) Mass spectral studies of YbCp,L and YbCpL2 (LH = acetylacetone 2,2,6,6-tetramethylheptane-3,5-dione 1,l,l-trifluoroacetylacetone benzoylacetone 4-benzoyl-3-methyl-l-phenyl-5-pyrazolone and trifluoroacetyl-a-thiophene) indicate that thermal disproportionation reactions occur to give YbCpf and YbLf The structures of [YbCp,Cl] and [YbCp2BrI2 have been determined and show a pseudo-tetrahedral arrangement of the two p-halide and two Cp ligands about Yb.168The magnetic properties of the complexes are explained by ligand field splitting of the Yb3+ free-ion 2F,,2 ground state and a small molecular field parameter.The first example of a ?r-bonded phosphacyclopentadienyl complex of a lan- thanide ion has been rep01ted.l~~ The complexes Ln(Me4C4P),(p-C1),Li(Sol),(Ln = Y Sol = MeOCH2CH,0Me; Ln = Lu Sol = OEt,) were prepared from LnC1 and LiPC,Me4. The complex with Ln = La could not be prepared. There is continuing interest in the synthesis and reactivity of lower oxidation state lanthanide compounds.The syntheses and solid state structures of the solvated Sm" complexes Cp,*Sm(0CSH8) (OCSH8 = dihydropyran) and SmCpq (OC5HI0) have been reported.'70 The disolvate exhibits a pseudo-tetrahedral coordination environ- ment around the Sm" ion whereas the monosolvate has a trigonal coordination environment counting the Cp* ring centroids as occupying single coordination sites. The unsolvated complexes LnCpq . (Ln = Eu or Sm) may be prepared from their diethyl ether adducts by heating to 100°C in toluene under reduced pressure."' The desolvated species LnCpT (Ln = Yb Sm) react with N20 to give (LnCpf),(p-0). The chalchogenide bridged complexes (YbCpT),(p-E) (E = S Se Te) were also prepared and exhibit no magnetic exchange across the chalchogenide bridge.The X-ray structure of (YbCp,*),(p-Se) reveals a near linear Yb-Se-Yb bridge (171.1') with the YbCp moieties mutually staggered about the bridge. The average Yb-Se distance is 2.621 A. Evidence for ethylene binding to EuCpT has been obtained from n.m.r. studies." Absolute metal-ligand bond disruption enthalpies have been measured for bis-pentamethylcyclopentadienylsamarium hydrocarbyl hydride dialkylamide alkoxide halide thiolate and phosphide cornple~es.'~~ Hydrocarbon functionaliz- ation by dinuclear Sm"/Sm"' oxidative addition is only expected to be exothermic in special cases. Alkyl halides are more reactive and YbCpTOEt undergoes atom- abstractive oxidative addition with the alkyl and aryl halides RX (R = hydrocarbyl) to give YbCpfX and YbCp*X2 along with Cp*H and R-R RH or R(-H) (ie.166 Z. Wu Z. Ye and Z. Zhou Polyhedron 1989 8 2109. 167 L. Yang L. Doi H. Ma and Z. Ye Organometallics 1989 8 1129. 168 H. Lueken J. Schmite W. Lamberts P. Hannibal and K. Hondrick Inorg. Chim. Acta 1989 156 119. 169 F. Nief and F. Mathey J. Chem. Soc. Chem. Commun. 1989 800. 170 W. J. Evans and T. A. Ulibarri Polyhedron 1989 8 1007. 171 D. J. Berg S. J. Burns R. A. Andersen and A. Zalkin Organometallics 1989 8 1865. 172 S. P. Nolan D. Stem and T. J. Marks J. Am. Chem. Soc. 1989 111 7844. Sc Y the Lanthanides and the Actinides ~lefins).'~~ This reaction is 103-106 times faster than typical d-block atom abstrac- tion reactions.YbCpf R is formed from radical trapping of R by the Yb" compound. This reacts further with YbCp;X in what are described as 'Yb'*'-Gringard' reactions. Mechanistic studies indicate the dominance of inner-sphere mechanisms in these reactions. Addition of C6F6 among other unsaturated fluorocarbons to YbCp? gives the mixed oxidation state complex Yb,(p-F)Cpt which has an asymmetric Yb"-F-Yb"' bond with Yb-F distances of 2.317(2) and 2.084(2) The two YbCpf moieties are mutually staggered about the Yb-F-Yb axis. The reactions of Sm" complexes with nitrogen containing organic substrates have also been investigated. SmCpft.h.f. reacts with pyridazine to give (~~CP*~.~.~.),[~,~]~-(CH=NNCH=CHCH-),], (12) in which a bridging bipyridazine moiety has formed through coupling at the 4-po~ition.l~~ Benzaldehyde azine PhHC=N-N=CH=Ph is also reductively coupled to give (SmCp,*),[p3 ,T~-(PhHC=N-N-CHPh-),I.Bipyridine reacts with SmCpft.h.f. to give the Sm"' complex SmCpf(r]2-N2CloH8). These compounds were all charac- terized by X-ray structural studies. Dimerization of the phosphaethyne derivative Bu+C=P has also been found in a reaction with SmCpft.h.f.2.176 This afforded (Cp,*Sm),(p-Bu'C=P-P=CBu') (13) in which the phosphaethyne moiety has dimerized and is bound to Sm via both the phosphorus and carbon atoms of the resulting diphosphabutadienyl moiety. Bu' -A phosphine oxide complex of Ybz+ has been prepared in the reaction between YbCp,(MeOCH,CH,OMe) and Ph3P0 which affords YbCp,(OPPh,) .177 The X-ray crystal structure of this compound reveals a pseudo-tetrahedral arrangement of the Cp and OPPh3 ligand groups about the Yb2+ion.The Yb-0 distances are unusually short at 2.30(2) and 2.33(2) A. Use of a diphenylphosphine substituted cyclo- pentadienide ligand has led to the synthesis of the heterobimetallic complex Yb(t.h.f.)2(C5H4PPh2)zPtMe2.t.h.f.178 The X-ray crystal structure reveals a pseudo tetrahedral environment about the Ybz+ ion comprising two oxygen atoms from the t.h.f. ligands and two r]5-C5H4PPh ligands. The -PPh2 moieties in turn bind to the PtMe moiety to give a near square planar environment around the Pt. Several compounds incorporating cyclo-octatetraenide ligands have been repor- ted. The sterically bulky ligand 1,4-( Me3Si),C,H;- reacts with YCl,(t.h.f.) to give 173 R.G. Finke S. R. Keenan and P. L. Watson Organometallics 1989 8 263. I74 C. J. Burns and R. A. Andersen J. Chem. SOC.,Chem. Commun. 1989 136. I75 W. J. Evans and D. K. Drummond J. Am. Chem. SOC.,1989 111 3329. 176 A. Recknagel D. Stalke H. W. Roesky and F. T. Edelman Angew. Chem. Int. Ed. Engl. 1989 28 445. 177 G. B. Deacon B. M. Gatehouse and P. A. White Polyhedron 1989 8 1983. 178 G.B. Deacon A. Dietrich C. M. Forsyth and H. Schumann Angew. Chem. Inr. Ed. Engl. 1989,28,1370. 108 C.J. Jones Y[ 1,4-(Me3Si),C8H,](CL-Cl),(t.h.f.), .22 The amide complex Li[ Lu( T~-C,H,BU)- (NMeCH2CH,NMe2),] has also been synthesized along with Li{Ln[ N(Me)CH,-CH2NMe2I4} (Ln = Y Ho Lu) and Li[YCp2(NMeCH2CH2NMe2)2].'79 The crystal structure of the holmium compound shows that two chelating NMeCH2CH2NMe2 ligands are bound to Ho3+ along with two monodentate amide ligands which also coordinate to Li (14).The reactions of Ln(C8Hg)Cl(t.h.f.) (Ln = Pr Sm Gd Tb Dy Er and Lu) with NaCp* affords Ln(CgH8)Cp*(t.h.f.),.180 The X-ray structure of the Lu complex reveals a slightly bent sandwich structure with the angle at Lu between the ring centroids being 173".Examples of formally Ln( 0) complexes have been obtained by co-condensation of atoms of the lanthanide elements with 1,3,5-tri-t-butylbenzeneto give the thermally stable bis( 7-arene)lanthanide( 0) sandwich compounds for the lanthanides Nd Tb Dy Ho Er and Lu.181 Thermally unstable complexes are obtained for La Pr and Sm and unisolable materials for Ce Eu Tm and Yb.This pattern was rationalized in terms of a bonding model in which the promotion energy from f"s2 to f"-ld's2 is an important factor. Where this energy is large stable complexes are not formed. The low stability of compounds of the early lanthanides despite their favourable electronic properties is attributed to the inability of the BU\C,H ligand to sterically saturate these larger ions. 4 Actinides This section is divided into two parts the first covers the general and coordination chemistry of the actinides and the second covers organoactinide chemistry. In the first of these parts the early actinides are considered first with compounds involving inorganic ligands and monodentate ligands preceding compounds with polydentate and macrocyclic ligands.The later actinides are included at the end of this part. In general lower oxidation state compounds appear after higher oxidation state compounds. General and Coordination Chemistry.-In a theoretical study iterative relativistic extended Huckel energy parameters are given for the elements Th to Np and the reasons why Tho has a bent structure and UO;' a linear structure are explored.'82 179 H. Schumann P. R. Lee and J. Loebel Chem. Ber. 1989 122 1897. 180 H. Schumann R. D. Kohn F. W. Reier A. Dietrich and J. Pickardt Organometallics 1989 8 1388. 181 D. M. Anderson F. G. N. Cloke P. A. Cox N. Edelstein J. C. Green T. Pang A. A. Sameh and G. Shalimoff J. Chem. Soc. Chem.Commun. 1989 53. 182 P. Pyykko L. J. Laakkonen and K. Tatsumi Inorg. Chem. 1989 28 1801. Sc Y the Lanthanides and the Actinides 109 In the synthetic field a new and convenient synthesis of UOBr3 by reaction of U03 with COBr2 has been described.23 The thermodynamically favourable elimination of CO provides a driving force for the reaction. The thermal decomposition of uranium and thorium carboxylates to form oxides has also been studied.'83 By varying the formulation of the precursor complex it is possible to control the composition of the oxides produced. A series of peroxothorates has been synthe- sized.'84 The compounds obtained include A,[Th(0,)F,(OH)2].nHz0 (A = NH4 n = 3; A = Na or K n = l) [Th2(02)3(C204)(H20)4]-5H20 and [Th,(o& (so& (H20)4].5H20.A route to phosphine oxide and arsine oxide complexes of UO',+ has been described in which U14 is oxidized by Me2S0 in MeC202Et.'85 This reaction affords U0214L2 [L = Ph3As=0 (Me2N)3P=0 (Me2N),C=O] and [Ph,P],[ U0214]. U0212L4 [L = Ph3As=0 (Me,N),P=O] can also be synthesized using this reaction. Some intercalation compounds of the actinides have been reported. These include [Cu( LL),],[ BA]~,-,~U02E04-2H20 (LL = 2,9-dimethyl-l,lO-phenanthrolineor 2,9-dimethyl-4,7-diphenyl-1,1O-phenanthroline; E = P As and x -0.2) in which the [Cu(LL),]+ quenches the uranyl photoluminescence.'86 The Cu' centres in these materials may be oxidized by Br then photochemically re-reduced. Dioxo-actinide(v1) ions can also form intercalates so that UO',+ or NpO;+ ions can be intercalated into HU02P04 or HNp02P04 to give layered hydrated ~olids.'~' In the aqueous reactions of AnO;+ with HAn02P04 (An = either U or Np in both reagents) the hydrated layered solids (AnO,),(PO4) are produced.Cross reactions involving two different actinides lead to substitution of actinide sites in the host lattice in addition to intercalation. The crystal structures of NMe4[U02S04~2H20]C1 and NH4[UO2F(SeO4)].H2O have been determined.'88*'89 Fast atom bombardment mass spectra of U02X2 (X = NO3 or CH3C02) have been obtained and provide evidence for the formation of oligomers (UO,) (n = 1 to 5) and 0 atom adducts (UO,),(O) (rn = 0 to 5) which pose interesting structural problems.'90 E.s.r. and magnetic studies of the Uv chloride derivative UCl,PPh3 indicate that a thermally accessible intramolecular electron transfer equilibrium exists according to equation (3):19' UVCI,PPh + U'"C1,PPh; (3) In solution studies the enthalpies and entropies of complexation of UO',+ and Th4+by aspartic acid have been determined.19' The results are in accord with actinide binding to only one carboxylate moiety in the amino acid.The effect of the substituent on the thermodynamic stability of 1:1 complexes of ten monosubstituted salicyclic acid derivatives with UO;+ has been studied in aqueous media.'93 In a 'H n.m.r. 183 K. M. Dunaeva and V. I. Sinitsyn Russ. J. Inorg. Chem. 1989 34 247. 184 C. B. Bhattacharjee M. K. Chaudhuri and R. N. D. F'urkayastha Znorg. Chim. Actu 1989 160 147.J. G. H. DuPreez and B. Zeelie Znorg. Chim. Actu 1989 161 187. 186 A. T. Jacob and A. B. Ellis Znorg. Chem 1989 28 3846. 187 P. K. Dorhout R. J. Kissane K. D. Abney L. R. Avens P. G. Eller and A. B. Ellis Inorg. Chem. 1989 28 2926. I 88 L. B. Serezhkina and V. K. Trunov Russ. J. Znorg. Chem. 1989 34 543. 189 V. A. Blatov L. B. Serezhkina V. N. Serezhkin and V. K. Trunov Russ. J. Znorg. Chem. 1989 34 91. 190 K. R. Jennings T. J. Kernp and P. A. Read Znorg. Chim. Actu 1989 157 157. 191 C. Miyake M. Hirose and H. Ohya-Nishigucti Znorg. Chim. Actu 1989 165 179. 192 A. Bismondo and L. Rizzo Polyhedron 1989 8 2233. 193 Y. Z. Yousif and F. J. M. A1 Imarah Transition Met. Chem. 1989 14 123. 110 C. J. Jones study of the kinetics of acac (acacH = pentane,2,4-dione) exchange between acacH and Th(acac) in CD3CN a deuterium isotope effect was found.’94 This is consistent with a proton transfer process being the rate determin-ing step.The mechanism of acetylacetonate substitution by P-diketonate in UO,[Me,C(O)CHC(Me)O],[( MeO),P=O] has also been studied.‘95 The syntheses and X-ray crystal structures of [N%][UO,(S,CNR~),] (R = Et R’ = (CH,), (CH,), Me2; R = Me R’ = Et) have been reported and all four complexes exhibit approximately hexagonal bipyramidal structure^.'^^ The equatorial s6 donor atom set is distorted from planarity by puckering to accommo- date the six large sulphur atoms. Interligand S-S distances are in the range 2.911(4)-3.109(4) A. The peroxo complexes [Th(o,)L] (L = C6H4(NH2)2-1,2; CSH4N(NH2)-2) [Th(02)C6H4(C02)2*20PPh,l,[Th(02)Li] (L’H = NH2CH2-CH20H and C6H4NH20H) [UO(O,),L] [UO(02)Lk] and [U0(O),LH20] (L”H2= HOCH2CH,CH20H and CH2(C02H),) have been prepared and found to oxidize PPh3 or AsPh3 to their corresponding 0~ides.l~’ In other work with bi- dentate ligands the complexes UO,L:(HL) (HL”’ = Ph,P(O)CH,C(O)Ph) and U02(U04),( HL’”),.2H20 were prepared.’98 The crystal structure of U02( NO3),( HL”’),! shows a distorted hexagonal bipyramidal coordination geometry about uranium with bidentate nitrate and HL”’ ligands bound uiu the phosphoryl oxygen.The bifunctional ligands (Pr’O),P( =O)CH,S( =O),R (R = C6Hll or C6H4Me-4 and n = 2; R = C6H,Me-4 and n = 1)and Ph2P( =O)CH,S( =0),NMe2 have also been prepared and their complexation reactions with U02( N03)2 investi- gated.’30 U02(NO,),{( Pr’0)2P(0)CH2S(0)2C6H contains a UO’,+ moiety equatorially coordinated to two bidentate nitrate ions and a phosphoryl oxygen from each of the two bifunctional ligands which bind in a monodentate manner.A series of Th4+ and UOz+ complexes containing Schiff base ligands has been de~cribed.’~~ The complexes are formulated as ThL2(N03)4 (L = N-(pyridine-2-carboxaldehyde)isonicotinylhydrazone,N-(pyridine-2-carboxalde-hyde)benzhydrazone (pcbh) N-(pyridine-2-carboxaldehyde)salicyoylhydrazone (pcsh) 3 N-(pyridine-2-carboxy1dine)aminophenol (pcap) and 4N-pyridine-2-carboxy1idene)aminoantipyrine U02L2( N03)2 (L = pcbh and pcsh) and U02-(pcap)(NO,) . The uranyl complexes U02(L)A [LH = S-methyl-1,Cbis-(salicylidene)isothiosemicarbazide,A = MeOH EtOH or Me,NCHO] have also been synthesized and the nature of the complex with A .= Me2NCH0 determined by an X-ray crystallographic study.200 An oxygen from the ligand A occupies an equatorial site in an approximately pentagonal bipyramidal coordination arrange- ment in which the four donor atoms of L also occupy equatorial sites about the trans-dioxo-uranium(v1) centre.In studies of compounds containing macrocyclic or cyclic polyether ligands the presence of benzo-groups or carboxylic acid substituents on crown ethers or of 194 N. Fujiwara T. NaKagawa H. Tomiyasu and H. Fukutomi Bull. Chern. SOC.Jpn. 1989 62 2087. 195 Y. Udagawa H. Tomiyasu W. S. Jung,T. Y. Eom and H. Fukutomi Bull.Chern. Soc. Jpn. 1989,62,2802. 196 N. W. Alcock and M. Pennington J. Chern. SOC.,Dalton Trans. 1989 471. 197 M. T. H. Tarafder M. B. H. Howlander B. Nath R. Khan and A. A. M. A. Islam Polyhedron 1989 8 977. 198 R. Babecki A. W. G. Platt J. C. Tebby J. Fawcett D. R. Russell and R. Little Polyhedron 1989,8 1357. 199 B. Kuncheria G. S. Devi and P. Indrasenan Znorg. Chirn. Acta 1989 155 255. 2oo V. M. Leovac E. Z. Iveges N. Galesic and D. Horvatic Znorg. Chirn. Acta 1989 162 277. Sc Y the Lanthanides and the Actinides alkyl substituents on diaza-crown ethers has been found to have only a small effect on the complexation of UOz+.201 The uranium crown ether complexes U02C12- (OH2)2L.L (L = 1,4,7,10-tetraoxacyclododecane)and U02C1,(OH2)(3,6,9,12,15-pentaoxaheptadecane- 1,17-diol) have been synthesized and their molecular struc- tures determined.202 The former complex contains two crown ether ligands only one of which is bound directly to the UO$+ ion by one of its oxygen atoms.The second crown ether molecule is hydrogen bonded to a coordinated water molecule as shown in Figure 17. In the latter complex the polyether is bound to the UO’,+ centre by one of the diol hydroxy groups. Again a coordinated water molecule is hydrogen bonded to internal ether oxygens in the diol. Both compounds contain an approximately pentagonal bipyramidal uranium centre with the equatorial donor atom set bound to the UO;’ core comprising two chlorides two water molecules and one oxygen from the polyether.C(9) A Figure 17 The structure of U0,C12(OH,),( 12-crown-4). 12-crown-4 (Reproduced by permission from J. Chem. SOC.,Chem. Commun. 1989 1586) Turning to the actinide elements in lower oxidation states thermal lensing spec- trometry has been applied to an investigation of the hydrolysis of U1+.’03 At 25 “C with 0 6 -log[H+] d 2.8 in 3 mole dm-3 (Na,H)ClO the data could be described by the following model U4+ + H,O U(OH)3++ H+ log*pl = -1.65(*0.05) (4) U4+ + 2H2O U(OH):+ + 2H+ lOg*p = <-4.5 (5) The UIV alkoxide complex UCl,(0CB~:)~(t.h.f.) has been prepared and may be used as a precursor to the compounds U(OCBu:),X [X = BH4 MeC(0)- CHC( Me)O v3-C3Hs CH2Ph].204 In addition the first structurally characterized neutral homoleptic aryl-oxo complex of UrVhas been de~cribed.~” An X-ray crystal structure reveals that U(O-2,6-Bu&H3) has a near tetrahedral U04 core with 201 J.Lagrange J. P. Metabanzoulou P. Fux and P. Lagrange Polyhedron 1989 8 2251. 202 R. D. Rogers M. M. Benning R. D. Etzenhouser and A. N. Rollins J. Chem. Soc. Chem. Commun. 1989 1586. 203 I. Grenthe G. Bidoglio and M. Omenetto Znorg. Chem. 1989 28 71. 204 C. Boudin and M. Ephritikhine J. Organomet. Chem. 1989,364 C1. 205 W. G. Von der Sluys A. P. Sattelberger W. E. Streib and J. C. Huffman Polyhedron 1989 8 1247. 112 C. J. Jones U-0 = 2.135(4)A and 0-U-0 angles of 110.2(1) and 108.0(2)". The U-0-C( ipso)angle is 154.0(6).6 In studies involving bidentate ligands it has been found that the extraction of La"' Ce"' Eu"' ThIV,and UIV from aqueous media into 4-methyl-2-pentanone containing 3-phenyl-4-acetyl-5-isoxazalone is greater than for related systems con- or taining l-phenyl-3-methyl-4-benzoyl-5-pyrazolone thenoyltrifluoroacetone as additives.206 Other UIV complexes which have been reported include UC14( 0-C6H4CH=NC6H4X-p) (n = 2,X = CI Br OH and Me; n = 3 X = One report of a complex of UIV with a macrocyclic ligand has appeared.Electrochemical and spectroelectrochemical studies of An(0EP) (acac) (An = U Th; OEPH = octaethylporphyrin; acacH = pentane-2,4-dione) reveal a reversible ring centred reduction process for both compounds.20g However whilst the Th complex also exhibits a first oxidation process associated with the porphyrin ring the U complex appears to undergo oxidation at the metal centre.There are two reports describing U"' compounds. Lewis base adducts of U13 have been found to offer a useful synthetic route to U"' complexes.209 The reaction of U turnings with I in t.h.f. affords UI,(t.h.f.) which has a pentagonal bipyramidal structure with one equatorial and two axial iodide ligands. This material reacts readily with anionic ligands X- to give UX,(t.h.f.) (X = N(SiMe,) or 2,4- dimethylpentadienyl and n = 0; X = CSHs or OC6H3Me,-2,6 and n = 1). In another study 'H n.m.r. measurements have shown that U(OC6H3Bu\-2,6) binds CNBu' to form U(OC6H3Bu\-2,6),(CNBu') which exchanges CNBu' with free ligand in solution via the intermediate U(OC6H3Bu\)3(CNBu') which may be detected at low Among papers describing the chemistry of the later actinides a report of the oxidation of Pd''to hIV by XeF and by SO,F-in 1 mol.dm- HC104 solutions has appeared.211 In both cases two molecules of Pu'I' are consumed per molecule of oxidant and mechanisms are proposed which involve a sequence of two one- electron steps since no evidence was found for the formation of pUv or hv1. The enthalpies of formation of 1 :1 complexes of Am'" with acetate and a series of aminocarboxylate ligands have been determined.,' The values obtained provide no evidence of significant differences in the bonding of Am"' Eu"' and Cm"' to the ligands studied. The solvent extraction of M3+ (M = Am Cm La Eu Lu) by thenoyltrifluoroacetone (Htta) in xylene has also been studied and evidence obtained for the extraction of M(OH)(tta) at higher pH values.213 Also of relevance to solvent extraction processes is a study of the protonation constants and stability constants with lanthanide ions of diethylene triamine-N,N,N',N"-tetraacetic acid-"'-propionic This ligand could provide a basis for separating Am3+ from lanthanides.206 A. Jyothi and G. N. Rao Polyhedron 1989,8 1111. 207 W. I. Azeez and A. I. Abdulla Transition Met. Chem. 1989 14 425. 208 K. M. Kadish Y. H. Liu J. E. Anderson A. Dormond M. Belkalem and R. Guilard Inorg. Chim. Acta 1989 163 201. 209 D. L. Clark A. P. Sattelberger S. G. Bott and R. N. Vrtis Inorg. Chem. 1989 28 1771. 210 W. G. Van der Sluys and A. P. Sattelberger Inorg. Chem. 1989 28 2496.211 R. L. Cook M. Woods J. C. Sullivan and E. H. Appelman Inorg. Chem. 1989 28 3349. 212 E. N. Rizkalla J. C. Sullivan and G. R. Chopin Inorg. Chem. 1989 28 909. 213 P. K. Mohapatra and P. K. Khopkar Polyhedron 1989 8 2071. 214 D. J. Sawyer and J. E. Powell Polyhedron 1989 8 1425. Sc Y the Lanthanides and the Actinides 113 0rganoactinides.-Some theoretical work on organolanthanides has appeared. Iter- ative relativistic extended Huckel energy parameters which give realistic metal orbital populations for organo-actinides are given for the elements Th to Np and energy levels are calculated for An(C8H,)z.'82 Quasi-relativistic Xa-Sw calculations on AnCp (An = U Th) which unlike AnCp,L (L = neutral two-electron ligand) in which all of the An d-orbitals are used as acceptors have a low lying dz2 orbital which competes with the 5f orbitals for metal electron^.'^^ Results for AnCp (An = Pa Np Pu)are also presented.Thermodynamic studies have examined the correlation between the standard enthalpies of formation for complexes of the type AnCpTL2 (An = Th'" or U'"; L = hydrocarbyl or OBu') and the enthalpies of formation of LH or LHn.'16 Also the effectiveness of U and Th complexes as catalysts for decoupling phenyl silane has been ~tudied.~'' ThCpr Me2 selectively catalyses the dimerization of phenyl silane in diethyl ether but the reaction with UCp:Mez is less selective and may involve U"' intermediates. Among the synthetic work reported a number of papers describe complexes involving Cp or related ligands.Treatment of triindenylthorium chloride with potassium metal in benzene affords tetraindenylthorium( IV)."~ No Th"' compounds were detected in this reaction. The reaction between U(BH,),.nt.h.f. and c~,*Th(pPh~)~ affords [Na(t.h.f.),][cp*(BH,),1 which contains chains of indepen- dent Cp*U(BH4) moieties.219 The three boron atoms and the Cp* ligand define an approximately tetrahedral coordination geometry about the U atom. The stoichiometry of the compound and black colour of the crystals suggest a mixed oxidation state species with an average U oxidation state of 3.5. In reactions involving monodentate hydrocarbyl ligands U(O-2,6-Bu:C6H,) reacts with LiCH(SiMe3)2 to give the royal blue complex U[CH(SiMe3)2]3.220 The X-ray structure of this com- pound reveals a pyramidal structure involving a y-agostic interaction with the silyl methyl groups.The reaction with CNBU' affords U(O-~,~-BU:C,H,)~(CNBU') which exchanges CNBu' with free ligand in solution via the intermediate U(OC6H3Bu~)3(CNBu')2 which may be detected at low temperature.'" The formation of a U-Si bond was achieved in the reaction between UCp,CI and LiSiPh which gave UCP,S~P~,.~~~ This compound in turn reacts with 2,6- Me2C6H3NC to give an insertion product UCp,[ C( NC,H3Me2-2,6)SiPh3] which contains an q2-isocyanide ligand. The reaction between UCp3[C( NC6H3Me2- 2,6)SiPh3] and HOSiPh affords UCp3(OSiPh3) which contains a near linear U-0-Si bond angle of 172.6(6)' and a short U-0 distance of 2.135(8) A. With OSiPh the three Cp ligands complete a distorted tetrahedral arrangement about the U atom.The chelating phosphorus ylide complexes AnCpgC1[CH2(CH2)PRR'] (An = U Th; R = R' = Me Ph; R = Me R' = Ph) have been prepared.222 'H 215 B. E. Burslen L. F. Rhodes and R. J. Strittmatter J. Am. Chem. Soc. 1989 111 2756. 216 A. R. Dias J. A. Martino Simiies C. Teixeira A. Airoldi and A. P. Chagas J. Organomet. Chem. 1989 361 319. 217 C. Aitken J. P. Barry F. Gauvin J. F. Harrod,A. Malek and D. Rousseau Organomeiallics 1989,8,1732. J. Goffart and S. Bettonville J. Organomet. Chem. 1989 361 17. R. R. Ryan K. V. Salazar N. M. Saver and J. M. Ritchey Inorg. Chim. Acta 1989 162 221. W. G. Van der Sluys C. J. Bums and A. P. Sattelberger Organornetallics 1989 8 855.M. Porchia N. Bnanese U. Cosellato F. Ossola G. Rossetto P. Zaneila and R. Graziani J. Chem. 218 219 220 221 SOC.,Dalton Trans. i989 677. 222 R. E. Cramer S. Roth F. Edelmann M. A. Bruck,K. C. Cohn and J. W. Gilje Organornetallics 1989 8 1192. 114 C.J. Jones n.m.r. studies of the Th'" compounds reveal dynamic behaviour for the ylide ligand involving Th-C bond breaking rotation and recombination processes. The X-ray structures of. UCp;Cl[CH,(CH,)PPhR] (R = Me; Ph) reveal an average U-C(y1ide) distance of 2.60 A as shown in Figure 18. The phosphinimine complex UCp?C12(HNPPh3) is formed in the reaction between UCpTCl and HNPPh3 .223 The X-ray structure of the molecule shows an agostic interaction between the uranium and the imino hydrogen and a U-N distance of 2.43A as shown in Figure 19.Figure 18 The Structure of UCpqCl[CH2(CH2)PPh2] (Reproduced by permission from Organometallics 1989 8 1192) Figure 19 The structure of UCpfC12(HNPPh,) (Reproduced by permission from OrganometaNics 1989 8 2327) R. E. Cramer S. Roth and J. W. Gilje Organometallics 1989 8 2327. Sc Y the Lanthanides and the Actinides Two reports describe complexes which contain a cyclo-octatetraenyl ligand or a derivative thereof. Th(C8H8)C12*n (t.h.f.)reacts with MgCp"C1t.h.f. to give Th(C9H8)Cp*Cl(t.h.f.),. Reaction of this compound with Bu'CH2MgC1 affords T~(C~H~)C~*(CL-C~)~M~~H~BU~ (t.h.f.) which desolvates at 100 "c to give [Th(C8H8)Cp*C1]2.224 This material in turn reacts with LiCH(SiMe3)2 to give Th(C8H8)Cp"[CH(SiMe3)2]7 the X-ray structure of which reveals the presence of V8-C8H8 and q5-C5Me5 ligands.The sterically bulky cyclo-octatetraenyl ligand 1,4-(Me3Si),C8H;- has been used to synthesize An[1,4-(Me3Si)&H& (An = Th U) from AnC14.22 The reaction of 1,4-(Me$i)2C&;- with UC12(BH4)2 affords U[ 174( Me3Si)2C8H,]( K~-BH,)~. T. M. Gilbert R. R. Ryan and A. P. Sattelberger Organometallics 1989 8 857.

ISSN:0260-1818    

DOI:10.1039/IC9898600077

出版商:RSC    

年代:1989

数据来源: RSC

摘要:

7 Radiochemistry By D. S. URCH Chemistry Department Queen Mary and Westfield College. Mile End Road London El 4NS 1 Introduction This section of Annual Reports will cover recent progress in radiochemistry but omit discussion of conventional properties of organic or inorganic substances which happen to be radioactive. General aspects of the subject are covered in Keller’s introductory text ‘Radiochemistry’,’ now available in English whilst current topics in radiochemistry have been reviewed2 in the second edition of ‘Isotopes Essential Chemistry and Applications’. A second edition of the classic ‘Chemistry of the Actinide Elements’ has also a~peared.~ An international conference4 on all aspects of radiochemistry was held in Mexico City in 1988 and a review has been published5 of the progress that has been made in the fifty years that have elapsed since the discovery of nuclear fission.2 Isotope Production 3H (Tritium).-Infra-red lasers have been used6 to enrich tritium containing molecules such as chloroform and dichloromethane whilst the tritium content of either liquid or solid hydrogen (deuterium) can be determined accurately7 by infra-red spectroscopy. Distillation (H20-3HH0)8and thermal diffusion (H2-3HH)9 have also been employed to enhance the tritium content of labelled molecules. “C.-When the [14N(p,a)’ ‘C] reaction is carried out in a nitrogen-hydrogen mixture (94.6%-5.6%) “C-methane is produced efficiently.” This proves to be a convenient first step in the production of carbon labelled radiopharmaceuticals.‘ C. Keller ‘Radiochemistry’ John Wiley and Sons New York USA 1981. ’J. R. Jones ‘Isotopes Essential Chemistry and Applications’ (RSC Special Publication No. 68) Royal Society of Chemistry London 1988. J. J. Katz G. T. Seaborg and L. R. Mom ‘Chemistry of the Actinide Elements’ Second Edition Methuen New York USA 1987. ‘7th Nuclear Chemistry Radiochemistry and Radiation Chemistry Symposium’ Institute Nacional de Investigaciones Nucleares Mexico City Zacatecas Univ. Mexico 1988. ’ L. Wiesner in ‘Jahrbuch der Atomwirtschaft’ 1989. ed. W. D. Muller and R. Hussner Verlagsgruppe Handelsblatt Dusseldorf Germany 1989 p. A55. K. Suzuki A. Yokoyama G. Fujisawa and N. Ishikawa Report (M-88-168) Japan Atomic Energy Research Institute Tokyo 1988.P. C. Souers E. M. Fearon R. K. Stump and R. T. Tsugawa Fusion Technol. 1988 14 850. A. Kaba R. Akai I. Yamamoto and A. Kanagawa J. Nucl. Sci. Technol (Tokyo) 1988 25 825. I. Yamamoto A. Matsuo and A. Kanagawa J. Nucl. Sci. Technol. (Tokyo) 1988 25 857. P. Landais and R. Finn Appl. Radial. hot. 1989 40 265. 117 118 D. S. Urch '*F.-The radioactive fluoride anion ["F]- is produced by the irradiation of "0 enriched water and considerable effort has been expended recently in optimizing target for its most efficient production. [18F]- can be removed from the aqueous solution in which it was made by electrochemical deposition on a carbon electrode,16 reversing the polarity liberates the labelled anion when required. Other reactions that have been used to produce "F are [19F(~,n)~'Fl'~ and the two-stage process that uses high energy tritons as intermediates [6Li(n,a)3H]-[ 160(3H,n)'8F].The latter process has the advantage that it can be initiated in a nuclear reactor,I8 no cyclotron or high energy accelerator is required. 22 Na.-This isotope can be produced by the deuteron bombardment of a magnesium target [24Mg(d,a)22Na] and then separated from the target material by ion exchange chromat~graphy.'~~~~ 28Mg.-Intermediate tritons are again involved in the production21 of this isotope by the neutron irradiation of lithium-magnesium alloys [26Mg(3H,p)28Mg] a photo- nuclear route has also been reported.22 Transition Metals-first ro~.-~~Fe with a very low "Fe contamination can be pro- duced by the a-particle bombardment of enriched chromium.23324 Isotopes of cobalt (57C0)and manganese (54Mn) are formed when a silver-iron target (56Fe enriched) is irradiated with deuterons.25 67 Ga.-This isotope can be produced26 by the proton irradiation of germanium targets that have been enriched with 70Ge and 72Ge and separated from the target material by heating to 1100°C in hydrofluoric acid vapour (a 'simple method' according to the authors!).72,73,75 Se.-The irradiation of arsenic (either as the element or oxide) with protons or deuterons initiates nuclear reactions which lead to the ejection of many neutrons and leave isotopes of ~elenium.~~,~' Optimum yields of 73Se were obtained with 3540MeV particles.29 'I 0. Solin J. Bergman M.Haaparanta and A. Reissel Appl. Radiat. Zsot. 1988 39 1065. l2 M. S. Berridge and R. Kjellstrom J. Labelled Compd. Radiopharm. 1989 26 188. l3 J. Bergman K. Aho M. Haaparanta A. Reissel and 0.Solin J. Labelled Compd. Radiopharm. 1989 26 143. l4 G. K. Mulholland R. D. Hichwa M. R. Kilbourn and J. Moskwa J. Labelled Compd. Radiopharm. 1989 26 192. T. J. Tewson M. S. Berridge L. Bolomey and K. L. Gould Nucl. Med. Biol. 1988 15 499. 16 D. Alexoff D. J. Schlyer and A. P. Wolf Appl. Radiat. Zsot. 1989 40 1. l7 G. A. Brinkman and A. Wyand Appl. Radiat. Zsot. 1988 39 1141. 18 S. Bulbulian F. de M. Ramirez J. L. Iturbe C. H. Collins and K. E. Collins Analyst 1989 114 349. 19 J. L. Q. de Britto M. A. V. Bastos R. F. da Silva and A. G. da Silva J.Radioanal. Nucl. Chem. Lett. 1988 127 31. 2o R. J. N. Brits and F. von S. Toerien Appl. Radiat. Isot. 1988 39 1045. 21 J. A. Velden Z. Kolar R. C. Vollinga and J. J. M. Goeiji J. Labelled Compd. Radiopharm. 1989,26,172 22 P. Polak A. Wijand and L.Lindner J. Labelled Compd. Radiopharm. 1989 26 173. 23 J. Zweit H. Sharma and S. Downey Appl. Radiat. Isot. 1988 39 1197. 24 P. Smith-Jones and R. Weinreich J. Labelled Compd. Radiopharm. 1989 26 159. '' P. M. Smith-Jones F. J. Haasbroek F. W. E. Strelow and R. G. Boehmer Appl. Radiat. Isot. 1988 39 1073. 26 A. F. Novgorodov A. Zelinski and A. Kolachkovski Radiokhimiya 1988 30,672. 27 A. Mushtaq S. M. Qaim and G. Stoecklin Appl. Radiat. Zsot. 1988 39 1085. 28 A. Mushtaq S. M. Qaim and G.Stoecklin J. Labelled Compd. Radiopharm. 1989 26 148. 29 R. Weinreich R. Schwarzbach Z. B. Alfassi and P. Smith-Jones J. Labelled Compd. Radiopharm. 1989 26 146. Radiochemistry 119 75Br.-When bombarded with helium-3 particles arsenic also looses neutrons thus [7'As( He,3n)7' Br] .30 *'Sr.-A similar type of process can be used to produ~e~'~~~ this positron emitting isotope of strontium from krypton [szKr(3He,3n)82Sr]. Transition Metals-second row.-A method for the production of 93m Nb by the decay of 93M0 and 93mM~ following the thermal neutron irradiation of 92M0 has been described.33 The heavier isotope of molybdenum 99M0,has been more extensively investigated as it is the precursor of 99mT~. A relatively simple way of producing it is from uranium fission products.34 Ion-exchange purification of labelled molybdate anions35 and the extraction of 99M0as a thiourea complex36 have both been reported recently.99mT~ can be obtained conveniently from the parent molybdenum isotope either by elution from a zirconium molybdate gel37 or by complex formation using methylethyl ketone.38 The radiochemical purity of 99mTc produced by such processes has been reviewed,39 with particular reference to the content of the long-lived isotope 99T~.40 When bombarded with very high energy a-particles molybdenum not only pro- duces isotopes of ruthenium with the loss of some neutrons4' but also a whole range of isotopes of other lighter elements 87Y,88,89Zr 90,92Nb 93M~, and 94,95,96Tc. 109 Cd is produced from '09Ag by deuteron bombardment of silver-iron targets.*' 125 Sb.-Neutron irradiation of tin leads to the formation of a P-emitting isotope which decays to '25Sb.Carrier free antimony42 can then be separated from the parent element using an anion exchange column. 10dine.-'~~I can be produced by the proton irradiation of either xenon43 or tel- lurium4 (123Te enriched [123Te(n,y)1231]). If tellurium-124 is bombarded with deuterons 1241is made.4' Techniques have been described46 for the extraction of the heavier isotope 13'1 from the fission products of uranium. 30 C. Loc'h and B. Maziere J. Labelled Compd. Radiopharm. 1989 26 169. 31 F. Tarkanyi S. M. Qaim and G. Stoecklin J. Labelled Compd. Radiopharm. 1989 26 153. 32 I. Huszar H.Youfeng J. Jegge and R. Weinrich J. Labelled Compd. Radiopharm. 1989 26 168. 33 A. D. Gedeonov and A. A. Nosov Zsotopenpraxis 1989 25 294. 34 R. 0. Marques P. R. Cristini D. P. Marziale E. S. Furnari and H. 0. Fernandez Bol. SOC.Argent. Radioprot. 1988 12 49. 35 (a) J. Buerck S. A. Ali and H. J. Ache Radiochim. Acta. 1989 46 151; (b) J. Buerck and A. H. A. Sameh 'Patent DE-3 616 391/A Germany (BRD) 1987. 36 S. A. C. Mestnik and C. P. G. da Silva Report PUB-248 Instituo de Pesquisas Energeticas e Nucleares Sao Paulo SP Brazil 1989. 37 Z. Aliludin M. Ohkubo and K. Kushita Report M-88-167 (Tokai Research Establishment) Japan Atomic Energy Research Inst. Tokyo 1988. 38 K. Svoboda Nukleon 1988 3 16. 39 E. Reich and K. W. Boegl Nuklearmedizin 1989 28 71.40 F. Budsky J. Prokop and F. Melichar Nukleon 1988 2 7. 41 M. K. Das B. R. Sarkar N. Ramamoorthy and R. S. M,ani Radiochim. Acta 1989 47 29. 42 Y. Maruyama and Y. Yamaashi Appl. Radiat. Zsot. 1988,39 1079. 43 (a) F. Tarkanyi Z. Kovacs S. M. Qaim and G. Stoecklin Radiochim. Acta 1989,47,25; (b)B. Scholten S. M. Qaim and G. Stoecklin J. Labelled Compd. Radiopharm. 1989,26,175;(c)R. Maag and A. Janett J. Labelled Compd. Radiopharm. 1989 26 171. 44 P. P. Dmitriev At. Ehnerg. 1988 64 118. 45 (a)R. M.Lambrecht M. Sajjad M. A. Qureshi and S. J. Al-Yanbawi J. Radioanal. Nucl. Chem. Lett. 1988 127 143; (6) H. L. Sharma J. Zweit A. M. Smith A. G. Smith and S. Downey J. Labelled Compd. Radiopharm. 1989 26 165. 46 N.D. Vaidya S. N. Shinde V. C. Nair and T. S. Murthy 'Radiochemistry and Radiation Chemistry Symposium' Department of Atomic Energy Bombay India 1988. 120 D. S. Urch Lanthanides.-When natural europium is bombarded with 100 MeV protons a range of gadolinium isotopes are formed47 (146,147&149 Gd) whilst the a-particle irradiation of holmium induces48 the [165H~(a,2n)'67Tm] reaction. Transition Metals-third row.-When samarium (144,147Sm), europium ("'Eu) or gadolinium (1s4,155Gd) targets are bombarded with neon (2",22Ne) nuclei49 in a cyclotron many new short lived isotopes of hafnium tantalum and tungsten are produced. The new atoms are removed from the production zone by a potassium chloride in nitrogen aerosol. 2.6GeV protons induce" a wide range of different spallation reactions in gold platinum and thorium targets producing radioactive isotopes of most of the elements in this row of the periodic table.Less exciting but arguably more useful is the development for radio-medical use of a Ix8Re generator based on potassium '88W-tungstate5' and also l9Irn Ir generatorss2 which utilize 19'Os (e.g. labelled potassium hexachloro-osmate absorbed on activated carbon52n). Heavy E1ements.-'O2Hg enriched mercury has been proposed44 as a target material for the production of 201T1 using proton bombardment. Such bombardment can also be used to produce bismuth isotopes from lead. After separation from the parent material these isotopes decay to give53 a good yield of '03Pb. The heavier '4n + 1' isotope of lead 211Pb can be isolated54 from the decay products of 219Rn,which in turn resulted from the decay of 223Ra (purified as the stearate).The heavier isotope of radium 228Ra can be extracted" from stocks of old thorium compounds by ion-exchange and electrolytic methods. A~tinides.-~~~h can be made56 by the alpha particle bombardment of highly enriched 235U,[235U( a,2n)237Pu]. The preparation of metallic berkelium (249Bk) albeit as a very thin film has been described57 and details of an ion-exchange procedure for the isolation of 250Bk from 254E~ have been given." Heavy ion bombardment of 238U(with l6O) and 242Pu (with "C) gives rise59 to isotopes of fermium (250Fm)and californium Cf). (2443245&246 47 N. A. Lebedev A. F.Novgorodov Ya. Slovak V. A. Khalkin and L. Ehkhn Radioisotopy. 1988,28,240. 48 F. Niu T. Ma and R. Teng J. Radioanal. Nucl. Chem. 1988 124 353. 49 (a) H. Bruchertseifer B. Eichler J. Estevez and I. Zvara Radiochim. Acta. 1989,47,41; (b)J. Estevez H. Bruchertseifer B. Eichler T. Kruz and I. Zvara Sou. Radiochern. 1988 29 751. so B. Szweryn W. Bruechle B. Schausten and M. Schaedel Radiochim. Acta. 1989 47 33. '' A. P. Callahan D. E. Rice and F. F. Knapp Jr. Nucl. Compact. 1989 20 3. 52 (a)C. Brihaye M. Guillaume and F. F. Knapp Jr. in 'Radioactive Isotopes in Clinical Medicine and Research' ed. R. Hoefer and H. Bergmann Schatteur Stuttgart Germany (BRD) 1988 p. 397; (b)C. Brihaye M. Guillaume S. Dewez F. F. Knapp Jr. D. E. Rice and A. P.Callahan J. Labelled Compd. Radiopharm. 1989 26 162. 53 T. N. Van der Walt and P. P. Coetzee Talanfa 1989 36 451. 54 R. W. Atcher A M. Friedman J. R. Huizenga and R. P. Spencer J. Radioanal. Nucl. Chem. Left. 1989 135 125. 55 L. D. Volynskii V. M. Garbuzov and V. A. Tsirlin Sou. Radiochem. 1988 29 629. 56 L. A. Pelevin A. D. Gedenov and B. N. Shuvalov Radiokhimiya 1988 30 806. 57 V. M. Radchenko A. G. Seleznev M. A. Ryabinin L. S. Lebedeva R. R. Droznik V. D. Shushakov V. A. Stupin and V. Ya. Vasil'ev Sou. Radiochem. 1988 29 549. 58 L. I. Guseva and V. V. Stepushkina Patent 1 293 889/A Moscow USSR 1985. 59 S. Usuda Report 1315 (JAERI Tokai Ibaraki) Atomic Energy Research Institute Tokyo Japan 1989. Rad iochemistry 121 3 Labelled Compounds Once produced it is necessary to incorporate radioisotopes into specific chemical compounds if they are to be of any use.By far and away the most important perceived use today is in nuclear medicine. The diagnostic potential of positron emitting isotopes and the medical desirability of short lived isotopes encourage nuclear physicists to seek out isotopes which combine these properties and stimulate chemists to invent rapid synthetic routes for their incorporation into ever more exotic compounds. Recent reviews conferences or symposia which have dealt with all aspects of or just some specific topics connected with the preparation of radiopharmaceuticals for use in nuclear medicine include ‘The 7th International Symposium on Radiopharmaceutical Chemistry’,60 a workshop ‘Synthesis and Application of Radioactively Labelled Organic Compounds’,61 a series of lectures under the general title ‘Isotopes Essential Chemistry and Applications’,2 a detailed review of radiopharmaceuticals labelled with short-lived isotopes62 and a discussion of future trends in radio pharmaceutical^.^^ This section of the Report will attempt to pick out recent developments in the production of labelled compounds which have some novelty or specific application and seek to eschew run-of-the-mill syn- theses of new labelled compounds by conventional routes and procedures.Tritium.-Tritium replacement of a halogen atom continues to be the most popular route to molecules labelled at a specific The general applicability of the method can be judged from the following by no means exhaustive list of compounds recently labelled in this way; ~trychnine,~~ hemimellitic betaxolol,66 ~iprofibrate,~~ acid,68 insulin,69 cadrala~ine,~’ ~hangrolin,~~ diter~alinium,~~ 2-deoxy-~-[2,6,6’-3H]gl~~ose,73 and nitrosoamino-pyridyl butanone derivative^.^^ The tech- nique is subject to many variations of both catalyst and conditions.Tritium gas is the normal reagent but the advantages of liquid or even solid tritium have been e~tolled’~ in the labelling of peptides and amino-acids radiation damage is low 60 ‘7th International Symposium on Radiopharmaceutical Chemistry’ Groningen Netherlands 1988. [published as J. Labelled Compd. Radiopharrn. 26 19891. 6’ Workshop ‘Synthesis and Application of Radioactively Labelled Organic Compounds’ Rossendorf Dresden Germany (DDR) 1988.62 G. Stoecklin in ‘Nuclear Medicine part IB Emission Computer Tomography with Short-lived Cyclotron Produced Radiopharmaceuticals’ ed. H. Hundeshagen J. Fitschen F. Helus K. Jordan D. Junker G. J. Meyer 0. Schober and G. Stocklin Springer Berlin Germany (BRD) 1988 p. 31. 63 M. Frier Med. Nucl. 1989 I 157. 64 D. E. Brundish and P. D. Kane J. Labelled Compd. Radiopharm. 1988 25 1361. 65 C. N. Filer and D. G. Ahern J. Labelled Compd. Radiopharm. 1989 27 309. 66 J. Allen and A. Tizot J. Labelled Compd. Radiopharm. 1988 25 931. 67 D. Johnston R. A. Ormiston and P. D. Slowey J. Labelled Compd. Radiopharm. 1988 25 1319. 68 M. Shimoni J. Azran and 0.Buchman J. Labelled Compd. Radiopharm. 1988 25 685. 69 A. Haensicke K. D. Kaufmann M. Beyermann J. Oehlke c‘. Kertscher M. Bienert H. Niedrich E. Mittag S. D. Bespalova and M. I. Titov Collect Czech. Chem. Commun. 1988 53 2936. 7n D. E. Brundish and P. D. Kane J. Labelled Cornpd. Radiopharm. 1988 25 1371. 7L P. Leon C. Garbay-Jaureguiberry S. Le Greneur R. Besselievre and B. P. Roques J. Labelled Compd. Radiopharm. 1988 25 1143. 72 X. Zhang Y. Bao and R. Ding Nucl. Tech. 1988 11 29. 73 J. Deschamps B. Rousseau and J. P. Beaucourt J. Labelled Compd. Radiopharm. 1988 25 1281. 74 J. Roemer J. Labelled Compd. Radiopharm. 1989 27 257. 75 J. C. Wiley Jr. D. H. T. Chien and N. A. Nungesser J. Labelled Compd. Radiopharm. 1988 25 707. 76 (a) C.T. Peng R. L. Hua P. C. Souers and P. R. Coronado Fusion Techno). 1988 14 833; (b) C. T. Peng R. L. Hua P. C. Souers and P. R. Coronado Report 97513 University of California Lawrence Livermore National Laboratory CA USA 1988. 122 D. S. Urch and neither peptide links nor aromatic rings are attacked. In the more conventional procedures palladium catalysts are often used (e.g. labelled pep tide^^^ or substituted purines78). Sometimes as in the preparation of labelled diester derivatives of bi~henyl,’~ a high-voltage discharge has proved effective. Tritiated water can be used as a source of tritium in catalysed exchange reactions as in the preparation” of [3H]-18-methylnogestrienon (10% Pd/C). Tritium gas can also be used directly to produce labelled compounds either by catalysed exchange (e.g.[3H]-desmethyl imipramine,81 arabino~y1-[6-~H]5-azacytosine~~) or by addition to a double bond. In the former case palladium oxide on barium sulphate proved an effective catalyst for the labelling of ~yronaridine~~ in solution. Tetramethyl- phra~ine~~ can be labelled in a similar way but using palladium on alumina and with the assistance of a microwave discharge. Such a discharge in tritium gas proved effective in the labelling of many steroids.85 Double bond reduction by tritium gas has the advantage that labelling takes place onl-y at specific sites. This procedure also benefits from catalytic assistance as in the production of labelled di-N- propylaminochromanes86 or ~-[3,4-~H,]ornithine.~~ Asymmetric tritiation leading to L-[~H]- N-a~etyltryptopophanamide,~~ has been accomplished using the rhodium- diPAMP complex as a catalyst.Other routes to labelled compounds can also involve reduction by the use of reagents such as tritiated sodium tetraborohydride. Compounds recently labelled in this way have included epoxide~,~~ prostaglandin^,^^ tetrahydroprot~berberines,~’ g-dea~inosine,~’and the juvenile hormone methyl [12 -3H]-( 10R)-10,11- epo~yfarnesoate.~~ Small reactive tritiated molecules are particularly valuable since they can be used to introduce a labelled group to a specific site in a larger molecule as part of a multi-stage synthesis. With this end in view new methods have been described for the preparation of high specific activity f~rmaldehyde~~ and also methyl iodide.95 2-bromo[ 1 -3H]ethano196 can be used to introduce labelled hydroxyethyl groups at sulphur or nitrogen sites.77 P. Pham A. Moustier. B. Rousseau and J. P. Beaucourt J. Labelled Compd. Radiopharm. 1988,25,901. 78 G. Cooper J. Bourrell M. Kaminek and J. E. Fox J. Labelled Compd. Radiopharm. 1988 25 957. 79 M. Yi S. Ding C. Zhang and J. Xie At. Energy Sci. Technol. 1987 21 212. 80 D. Wu S. He and Y. Ge J. Isof. 1988 1 50. 81 J. Exner K. Fuksova R. Krulik D. Pichova and J. Picha Radioisotopy 1988 29 178. 82 G. F. Taylor K. Zamani and J. A. Kepler J. Labelled Compd. Radiopharm. 1988 25 1073. 83 S. Jiang L. Zhang D. Zheng Z. Feng and Z. Wu Nucl. Tech. 1987 10 44. 84 S.Ding Z. Meng Z. Han and Y. Jin J. Nucl. Radiochem. 1988 10 42. 85 G. Z. Tang and C. T. Peng J. Labelled Compd. Radiopharm. 1988,25 585. 86 J. M. Cossery L. Pichat C. Perdicakis G. Coudert and G. Guillaumet J. Labelled Compd. Radiopharm. 1988 25 833. 87 V. Tolman Radioisotopy 1988 29 183. 88 H. Pinto-Alphandary C. Van Craeynest-Jimonet J. L. Morgat and P. Fromageot J. Labelled Compd. Radiopharm. 1988 25 1273. 89 F. Setiabudi F. Oesch and K. L. Platt J. Labelled Compd. Radiopharm. 1988 25 1209. 90 V. P. Shevchenko T. Y. Lazurkina and N. F. Myasoedov Radiokhimiya 1988 30,527. 9’ X. Zhang and L. Yang Nucl. Tech. 1988 11 24. 92 A. K. Singh and R. S. Klein J. Labelled Compd. Radiopharm. 1988 25 1219. 93 E. Wai-si and G. D. Prestwich J.Labelled Compd Radiopharm. 1988 25 627. 94 M. Coppo B. Rousseau and J. P. Beaucourt J. Labelled Compd. Radiopharm. 1988 25 921. 95 P. Parent Thesis ‘Synthesis of High Specific Activity Tritium Labelled Compounds’ Conservatoire National des Arts et Metiers (Dept. Biologie) Paris France 1986. 96 M. Verny and C. Nicolas J. Labelled Compd. Radiopharm. 1988 25 949. Radiochemistry 123 Two mechanistic studies have been reported on the tritium labelling process. The first97 concerns the ferric chloride catalysed exchange reaction between tritiated water and the aromatic hydrogens in benzene and toluene. During the initial stages of the reaction tritiation proceeded preferentially at the ortho-and para-positions in tolulene at rates about two hundred times faster than in benzene.The second was a theoretical investigation of the role of metallic catalysts in the Wilzbach gas exposure labelling method. Carbon.-Techniques for the preparation of molecules labelled with 1C99 and with 14C100 have been reviewed. The former because of its twenty minute half-life poses the greater challenge to the synthetic chemist. Hot-atom reactions within the cyclo- tron can lead to "C being produced"' as labelled carbon dioxide. This can either be used directly (e.g.by reaction with trimethylsilyl derivatives followed by lithium aluminium hydride reduction to give "C-methyl as in the syntheses of the labelled D receptor antagonist SCH 23390102 and [1'C]-chlorpromazine;'03or via a Grignard reaction to form acetate which can then be used to form ["Clacetyl coenzyme A)'04 or converted to that most versatile of intermediates "C-methyl iodide.This reagent has been used to label many large and complex molecules for diagnostic studies in nuclear medicine thymidine,lo5 N-["Clmethyl labelled sertraline,lo6 nomifen- sine,lo7 and pyrilaminelo8 as well as a dopamine D receptor antagoni~t'~' and the benzodiazepine receptor antagonist Ro 15-1788."O A method for the rapid prepar- ation of ''C-labelled nitroalkanes,' ' ' especially nitromethane,' l2 has been described. These compounds can be used in further reactions such as the synthesis of ~-[1- "C]glu~ose."~ Other molecules that have been labelled with "C have included [3-"C]propionic acid,'14 sodium thiocyanate,"' [isopropyl-"C]nimodipine,"5 91 K.Oohashi K. Mori and K. Hirano J. Radioanal. Nucl. Chem. Lett. 1989 135 419. 98 Z. Meng S. Ding B. Liu and Y. Jin J. Nucl. Radiochem. 1988 10 180. 99 C. Crouzel Report Conference 9631 Centre d'Etudes Nucleaires de Saclay 91 Gif-sur-Yvette France 1988. 100 L. Pichat Radioisotopy 1988 29 9. 101 T. J. Ruth K. Pedersen C. Morin G. Ryley and C. Morrison J. Labelled Compd. Radiopharm. 1989 26 460. 102 S. Ram R. E. Ehrenkaufer and L. D. Spicer Appl. Radiat. hot. 1989 40 425. 103 S. Ram and L. D. Spicer Appl. Radiat. Isot. 1989 40 413. 104 G. Mannens G. Slegers R. Lambrecht and P. Goethais J. Labelled Compd. Radiopharm. 1988,25 695. 105 E. Poupeye A. de Leenheer G. Slegers P. Goethais and R. E. Counsell Appl.Radiat. Zsot. 1989,40 57. 106 M.-C. Lasne V. W. Pike and D. R. Turton Appl. Radiat. Isot. 1989 40 147. 107 J. Ulin A. D. Gee B. Laangstroem P. Malmborg and J. Tedroff Appl. Radiat. Isot. 1989 40,171. I 08 K. Yanai R. F. Dannals A. A. Wilson H. T. Ravert U. Scheffel S. Tanada and H. N. Wagner Jr. Nucl. Med. Biol. 1989 15 605. 109 A. A. Wilson R. F. Dannals H. T. Ravert and H. N. Wagner Jr. Appl. Radiat. Isot. 1989 40 369. 110 C. Halldin S. Stone-Elander J.-0. Thorell A. Person and G. Sedvall Appl. Radiat. Zsot. 1988,39,993. 111 K.-0. Schoeps S. Stone-Elander and C. Halldin Appl. Radiat. Zsot. 1989 40 261. 112 K.-0. Schoeps C. Halldin S. Stone-Elander T. Greitz and B. Laangstroem J. Labelled Compd. Radiopharm. 1988 25 749. 113 K.-0.Schoeps C. Halldin J.-O. Thorell S. Stone-Elander G. Blomqvist and L. Widen J. Labelled Compd. Radiopharm. 1989 26 86. 114 K. Niisawa K. Ogawa T. Nozaki and T. Hara J. Labelled Compd. Radiopharm. 1989 26 64. 11s S. Stone-Elander P. Roland C. Halldin E. Schwenner H. Boeshagen L. Widen and A. G. Bayer J. Labelled Compd. Radiopharm. 1989 26 238. 124 D. S. Urch amino acids,"6 and acyl chloride~."~ Carbon-1 1 can be introduced into aromatic rings using aryl chromium tricarbonyl intermediates.' l8 The preparation of 14C-labelled compounds continues apace but utilizing the standard procedures of synthetic organic chemistry. Even so it is of interest to note the study"' made of the alkali malonate catalysed exchange between 14C02 and carboxyl groups work undertaken to assess the utility of this reaction for the production of "C-acids.Nitrogen.-Despite a half-life of only ten minutes it has proved possible to incorpor- ate 13N into a couple of compounds butylamine12' and an opioid peptide.121 Oxygen.-The two minute half-life of "0 mitigates against much conventional chemistry but catalytic methods have been developed122 to convert 150-oxygen to 15 0-carbon dioxide. It is also possible to design systems for the production of 15O-~ater'~~ and even ['s0]b~tano1.124 Fluorine.-**F labelled fluorine gas produced by nuclear reactions in neon can be used directly to produce labelled compounds or introduced into electrophilic or nucleophilic reagents. In the former case site specificity can be achieved by the positioning of labile groups such as trimethylsilyl where required (e.g.N-['sF]fluoropyridinium triflate12'). In the absence of such direction fluorine gas gives rise to a much more random distribution of 18F than a reagent such as acetyl hypofluorite as experiments with phenylalanine tyrosine and dopamine have shown.'26 Recently a novel sequence of reactions has been rep~rted"~ which rapidly convert some "F-fluorine into the acetyl hypofluorite and the remainder into a tetra-alkylammonium fluoride thus neatly producing reagents for both electrophilic and nucleophilic reactions. Whilst "F-acetyl hypofluorite is quite selective in its reactions with aromatic rings producing 2-18F-phenylalanine 3-'8F-tyrosine,1267'28 and 2-"F-d0pa'~~ from unfluorinated starting materials the site for electrophilic attack can be directed by metallation using either tin or mer~ury,'~'as in the recently reported synthesis of ~-64 18F]fluorodopa.'30 Acetyl hypofluorite has also proved useful in producing'31 labelled derivatives of antitumor agents.116 (a) T. Guddat W. Herdering A. Knoechel and 0. Zwernemann J. Labelled Compd. Radiopharm. 1989 26 79; (b) K. J. Fasth G. Antoni P. Malmborg and B. Laangstroem J. Labelled Compd. Radiopharm. 1989 26 88. 117 S. K. Luthra D. Le Bars V. W. Pike and F. Brady J. Labelled Compd. Radiopharm. 1989 26 66. 118 M. J. Adam J. A. Balatoni and L. D. Hall J. Labelled Compd. Radiopharm. 1989 26 72. J. Szammer E. Simon-Trompler and L. Oetvoes J. Radioanal.Nucl. Chem. Lett. 1989 135 125. 120 G. W. Kabalka J. F. Green W. Zhe and M. M. Goodman J. Labelled Compd. Radiopharm. 1989,26 90. 121 H. Saji D. Tsutsurni J. Konishi A. Yokoyama Y. Kiso and T. Mimoto J. Labelled Compd. Radiopharm. 1989 26 73. 122 (a) R. Iwata T Ido Y. Fujisawa and S. Yamazaki Appl. Radiat. Isor. 1988 39 1207; (b) R. Iwata S. Yamazaki Y. Fujisawa and T. Ido J. Labelled Compd. Radiopharm. 1989,26,157; (c) K. Strijckmans J. Sambre and F. Guchteneire J. Labelled Compd. Radiopharm. 1989 26 458. 123 Y. Miyake Y. Ichiya Y. Kuwabara M. Otsuka M. Wada and K. Masuda Kaku Igaku 1988,25,659. 124 G. W. Kabalka J. F. Green and G. McCollum J. Labelled Compd. Radiopharm. 1989 26 76. 125 F. Oberdorfer E. Hofmann and W.Maier-Borst J. Labelled Compd. Radiopharm. 1988 25 999. 126 H. H. Coenen K. Franken P. Kling and G. Stoecklin Appl. Radial. Isor. 1988 39 1243. 127 R. Chirakal G. Firnau and E. S. Garnett Appl. Radiat. Isot. 1988 39 1099. 128 M. Murakami K. Takahashi and Y. Kondo J. Labelled Compd. Radiopharm. 1988,25,773. 129 A. Luxen M. Perlmutter and J. R. Barrio J. Labelled Compd. Radiopharm. 1989 26 1. 130 M. J. Adam and S. Jivan Appl. Radiat. Isor. 1988 39 1203. 131 G. W. M. Visser A. T. Bijma J. A. R. Dijksman and J. D. M. Herscheid Appl. Radiat. Isor. 1989,40 47. Radiochemistry 125 Nucleophilic substitution using 18F- can be achieved by nitro group displacement (as in the preparation of ['8F]ritanserin132), by mesylate group displacement (a step in the production of ['sF]fluorothienylcyclohexylpiperidine'33),or by the newly developed method of replacement of a cyclic sulphamate (a technique used in the synthesis of labelled fluoro-analogues of N-methyl-~-aspartate'~~).A very con- venient way of handling the radioactive fluoride anion is for it to be adsorbed onto an aminopolyether resin'35 (Kryptofix 222). This has led to new synthetic routes for 2-deoxy-2-[ '8F]fluoro-~-galactose'36 and 3-[ "F]fluoro-1-( 2-nitro-l-imidazolyl)-2-propan01,'~~ being reported. Sulph~r.-~~S-methionine has proved a useful starting material for the preparation of labelled hornocy~teine'~~ and glycyrrhizic acid'39 derivatives whilst [35S]thiourea was used to introduce sulphur-35 into 2-mercaptobenzimidazoles.'40The preparation has also been reported of 35S-thiophosphate'41 and its incorporation into inositol triphosphate.Transition Metals-first row.-The preparation of 57C0labelled thyroxine'^^ and of [67Cu]cupric-bis(thiosemicarbazones)'43 for radioimmunoassay and for use as radiopharmaceuticals has been reported. Gallium.-The preparation of a series of 68Ga labelled radiopharmaceuticals has been reviewed,I4 with special reference to bifunctional molecules in which one section chelates with the gallium whilst another part has a specific biochemical role. Bromine.-82Br can be introduced into many organic molecules by the addition of [82Br]bromine to a double bond'45 or by aluminium trichloride catalysed exchange with labelled dioxane dibr~mide.'~~ In bromamine-T it was that bromide exchange was maximized at pH 2.A report has appeared recently'48 which describes methods for the preparation of molecules (e.g.bromospiperone and bromolisuride) labelled wth lighter short-lived positron emitting isotopes 75Br and 76Br. Yttrium.-Tumour associated monoclonal antibodies have been labelled with 90Y.149 132 C. Crouzel A. Denis M. Venet and G. Sanz J. Labelled Compd. Radiopharm. 1988 25 827. 133 D. 0. Kiesewetter K. C. Rice M. V. Mattson and R. D. Finn J. Labelled Compd. Radiopharrn. 1989 27 277. 134 (a) D. M. Wieland M. R. Kilbourn D. J. Yang E. Laborde D. L. Gildersleeve M. E. Van Dort J.-L. Pirat B. J. Ciliax and A. B. Young Appl. Radiat. Zsot. 1988 39 1219; (b) F. Brady S. K. Luthra and V.W. Pike Appl. Radiat. Isot. 1989 40 325. 135 P. M. Pojer Aust. NZ J. Med. 1988 18 490. I36 T. Haradahira M. Maeda Y. Kai and M. Kojima J. Labelled Compd. Radiopharm. 1988 25 721. 137 D.-R. Hwang C. S. Dence T. A. Bonasera and M. J. Welch Appl. Radiat. Isot. 1989 40 117. 138 K. Hamacher J. Labelled Compd. Radiopharm. 1989 27 344. 139 L. A. Baltina R. M. Kondratenko Yu. G. Kuvatov Yu. I. Murinov and G. A. Tolstikov SOC.Radiochem. 1988,30 271. 140 D. R. Doerge J. Labelled Compd. Radiopharm. 1988 25 985. 141 P. Folk E. Kmonickova L. Krpejsova and A. Strunecka J. Labelled Compd. Radiopharm. 1988,25,793. 142 S. Al-Awadi K. Adham M. Hassan and H. Abdul-Dayem J. Immunol. Methods 1988 108 27. 143 M. A. Green and E. John J. Labelled Compd.Radiopharm. 1989 26 351. 144 M. J. Welch Progress Report DOE/ER-60 512-3 Department of the Environment Washington DC USA 1989. 145 R. Otto Report TR2373 Centre d'Etudes Nucleaires de Saclay 91 Gif-sur-Yvette France 1988. 146 R. Otto Report TR2374 Centre d'Etudes Nucleaires de Saclay 91 Gif-sur-Yvette France 1988. 147 (a)V. R. S. Rao G. Erdtmann and H. Petri J. Radioanal. Nucl. Chem. Lett. 1989 135 247; (b) V. R. S. Rao G. Erdtmann and H. Petri J. Radioanal. Nucl. Chem. Lett. 1989 135 257. 148 C. Loc'h Thesis Conservatoire National des Arts et Metiers 75 Paris France 1988. 149 S. J. Mather D. M. Tolley and G. W. White Eur. J. Nucl. Med. 1989 15 307. 126 D. S. Urch Technetium.-The nuclear properties of 99mTc make it one of the most widely used isotopes in nuclear medicine.The relationship between its varied chemistry and possible radiopharmaceuticals has been extensively re~iewed.'~' Problems associated with the stability of technetium compounds have also been addressed.'" The use of specific types of technetium compounds in nuclear medicine has been discussed; nitrodo-c~mplexes,'~~ bi-and tri-dentate Schiff's bases,'53 and tetradentate bisaminobisthiol cornplexe~.'~~ In all cases the technetium originally present as the Tc"" pertechnate anion must be reduced before complex formation can take place. Stannous chloride is widely used -a cunning new te~hnique'~~ requires the pertech- nate solution to flow through a plastic tube the inner surface of which is covered with adsorbed stannous ions.Although the final oxidation state of the technetium is often not well established complexes of aminohippuric acids,156 salicyclic acid,15' cysteine,lS8 substituted iminodiacetic and gentamycin'60 have been prepared and used successfully. Other methods for the reduction of Tc valency have included sodium borohydride in the formation of phosphonate'61 and thiodiglycollic acid'62 complexes and electrochemical methods leading to complexes based on dithi01s.l~~ The preparation of many other complexes containing Tc- S bonds has been reported thioether~,'~~rnonothi0-/3-dicarbonyls,'~~2,3-dimercaptos~ccinates,'~~2,3-dithiophosphosuccinates etc.16' Attempts to determine the technetium valency in some of these complexes have been made by comparing the UV spectra of complexes made from 'reduced pertechnate' and from technetium chlorides of known stoichiometry.'68 Technetium can also be used to label much larger molecules such as To this end the development of bifunctional ligands which can both bind to the 150 (a) H.Spies and R.Muenze Med. Nucl. 1989 1,125; (b) K. Schwochau in 'Proceedings of the 2nd International Symposium on Technetium Chemistry and Nuclear Medicine' ed. M. Nicolini G. Bandoli and U. Mazzi Raven Press New York U.S.A. 1986 p. 103; (c) B. Johannsen Isotopenpraxis 1988 24 449. 151 L. R. Chervu B. D. Vallabhajosyula S. B. Chun and J. Mni J. Nucl. Med. Allied Sci. 1988 32 234. 152 J. Baldass J. Bonnyman and J. Kanellos see ref. 150 (b) p. 103. 153 (a) G.Bandoli and M. Nicolini ibid. p. 73; (b) A. Duatti A. Marchi L. Magon J. L. Vanderheyden and E. Deutsch ibid. p. 131. 154 A. D. Watson T. H. Tulip and D. C. Roe Ibid. p. 61. 155 D. J. Maddalena G. M. Snowdon A. Awaluddin and P. M. Pojer in 'Proc. 5th International Symposium on Radiopharmacology' ed. A. E. A. Mitta C. 0. Canellas and R. A. Caro Comision Nacional de Energia Atomica Buenos Aires Argentina 1987 p. 75. 156 (a) B. Zmbova D. Djokic V. Bogdanova I. Tadzer B. Ajdinovic and M. Rastovac Appl. Radiat. Isot. 1989 40 225; (b) K. K. Bhargava Z. Zhuangyu S. B. Chun L. R. Chervu and M. D. Blaufox J. Labelled Compd. Radiopharm. 1988 25 943. 157 T. Soldi M. T. Valentini Ganzerli and M. DiCasa see ref. 150(b) p. 135. I58 A. H. Al-Kouraishi J.Radioanal. Nucl. Chem. 1988 125 213. 159 M. G. Arguelles C. 0.Canellas A. E. A. Mitta A. S. Leon E. S. Verdera and E. Leon ref. 155 p. 188. 160 S. H. Al-Kouraishi J. Radioanal. Nucl. Chem. 1988 125 203. 161 W. R. Heineman E. Deutsch and B. Scott in 'Proceedings of the 2nd International Symposium on Technetium Chemistry and Nuclear Medicine' ed. M. Nicolini G. Bandoli and U. Mazzi Raven Press New York USA 1986 p. 97. 162 S. A. Balakrishnan P. M. Pandey S Gaitonde and R. S. Mani ref. 150(b) p. 97. 163 I. De Gregori and S. Lobos Appl. Radiat. Isot. 1989 40 385. 164 G. F. E. Morgan J. Pope J. R. Thornback and A. E. Theobald ref. 150(b) p. 65. 165 H. Spies U. Abram R. Munze E. Uhlemann E. Ludwig and D. Scheller ref. 15O(b) p. 137. 166 H.Spies and D. Scheller ref. 150(b) p. 141. 167 S. Kovacheva and R. Georgieva Rentgenol. Radiol. 1987 26 32. 168 R. Stella and M. T. G. Valentini Appl. Radiat. Isot. 1988 39 1125. 169 D. Blok R. 1. J. Feitsma M. N. J. M. Wasser and E. K. J. Pauwels Nucl. Med. Biol. 1989 16 11. Radiochemistry 127 protein and chelate to technetium is most imp~rtant.'~' The labelling of both leukocyte^'^^ and fibrin~gen'~~ has been reported recently. with 99mT~ Ruthenium and Rhodium.-When ['03Ru]ruthenium trichloride reacts with ferrocene haloperidol the corresponding labelled ruthenocene compound is formed.'73 This decays to ['03mRh]rhodocene haloperidol which is rapidly oxidized in air to [103m Rhlrhodocinium halperidol. Indium.-" 'In is widely used to label monclonal antib~dies.'~"'~ The slightly heavier isotope '13"In (~~,~99.5 m) forms a complex with 3,3,10,10-tetraethyl-1,2-dithio-5,8-diazacyclodecanehydrochloride175which can be used as a myocardial imaging agent.10dine.-'~~I made by the [124Te(p,2n)'231] reaction'76 is widely used for the labelling of iodo-compounds by exchange with the iodide anion as in the preparation of [1231]rn-iodobenzylguanidine'77 and 154p-['231]iodophenyl)pentadecenoic or even the much larger glucose channel blocking agent MK-801.'34a In some cases as in the labelling of 2,5-dimethoxy-4-iodophenylisopropylamine,179 chloramine-T must also be used as an oxidant; the procedure is found to work equally well with 1231 and 1251. This method was also used in the preparation of 5-['251]iodo- ochratoxin.180 Iodide exchange at aromatic ring sites can be catalysed by transition metal ions.The mechanism of this reaction has been investigated181 and the results compared with CND0/2 based predictions. Procedures for the preparation of labelled amines 6413'I]iodohexylamine'82 or (*)-(4-[ '3'I]iodophenyl)pentyl-by iodide attack at a hydroxyl site have been developed with the assistance of trimethylsilyl polyphosphate or thallium trifluoroacetate. A new synthesis has also been reported'84 of [13' Iliodomethane. Heavier Elements.-Methods have been described whereby monoclonal antibodies can be labelled with '53Sm 185 or 203Pb.'86 Also details for the preparation of a I70 S. Z. Lever K. E. Baidoo A. V. Kramer and H.D. Burns Tetrahedron Left. 1988 29 3219. 171 (a) H. Kelbaek J. Linde and S. L. Nielsen Eur. J. Nucl. Med. 1988 14,620; (b) G. Endert U. Franke and P. Kleinert Med. Nucl. 1989 1 11. 172 M. G. Noto G. Rabiller C. Garrie Faget C. Fisman and A. Manzini ref. 155. p. 202. 173 M. Wenzel and Y. Wu Appl. Radiat. Zsot. 1988 39 1237. 174 (a) R. Reilly S. Houle K. Sheldon and A. Marks Appl Radiat. Isof.,1989,40,279; (b)A. M. Zimmer J. M. Kazikiewicz S. M. Spies and S. T. Rosen Nucl. Med. Biol. 1989 15 717; (c) M. Hartikka P. Vihko L. Hakalahti P. Torniainen R. Vihko and M. Soedervall Eur. J. Nucl. Med. 1989 15 157. 17s B. Liu Y. Jin L. Zhu M. Meng Y. Shi and H. F. Kung J. Nucl. Radiochem. 1988 10 162. 176 M. Sajjad R. M.Lambrecht and S. A. Bakr Nucl. Med. Biol. 1989 15 721. 177 B. H. Mock and R. E. Weiner Appl. Radiat. hot. 1988 39 939. 178 (a) M. Sajjad R. M. Lambrecht and S. Bakr Appl Radiat. Isot. 1989 40 428; (b) R. F. Verbruggen Appl. Radiat. Isot. 1988 39 1097. 179 C. A. Mathis A. T. Shulgin A. J. Hoffman and D. E. Nichols J. Labelled Compd. Radiopharm. 1988 25 1255. 180 D. Schmiedova B. Cerny and K. Veres Radioisotopy 1988 29 102. 181 T. Li Z. Meng X. Chang and S. Zheng Chin. J. Nucl. Sci. Eng. 1987 7 305. 182 G. Gopalokrishnan Y. W. Lee S. Selvaraj D. N. Abrams A. A. Noujaim and S. F. P. Man J. Labelled Compd. Radiopharm. 1988 25 879. 183 Y. W. Lee G. Gopalakrishnan S. F. P. Man and A. A. Noujaim J. Labelled Compd. Radiopharm. 1988 25 609.184 C. J. Cayetano F. P. Ramirez and M. E. Cortes ref. 4 p. 80. 185 M. E. Izard G. R. Boniface P. Sorby and K. Z. Walker Aust. NZ 1. Med. 1988 18 510. 186 S. C. Srivastava R. C. Mease G. E. Meinken L. F. Mausner and Z. Steokewski Report 41 800 Brookhaven National Laboratory Upton NY USA 1988. 128 D. S. Urch series of phosphonate derivatives of 186Re have been given.187 Tetramethyl lead labelled with 'loPb can be preparedIg8 by the electrochemical reduction of methyl iodide using a radioactive lead coated cathode. Subsequently trimethyl [*"Pb]lead chloride was also synthesized. Proteins have been successfully labelled with astatineIg9 by the expedient of first allowing the astatine (*"At) to react with a suitable organic reagent e.g.diazo-p-aminobenzoic acid and subsequently conjugat- ing the labelled complexes with the protein. 4 Hot-Atom Chemistry This section will consider chemical reactions of atoms and ions that have been excited translationally or electronically by nuclear transformations. The whole field since the discovery of the first such reaction by Szilard and Chalmers has recently been reviewed'" and the specific application of reactions of this type for the production of labelled molecules has been a~sessed."~ 3H.-The hot atom reactions of tritium in graphite,'92 boron carbide,193 and copper tetraphenylp~rphyrin'~~ have been investigated. In the first two cases hydr~gen''~~ and the annealing temperature had a critical effect upon the chemical state of the tritium.With the porphyrin attempts were made by the addition of helium as moderator to demonstrate that the relative energies of the tritium atoms substituting at aromatic sites were higher than those reacting at pyrrole sites. A similar type of comparison in which the reactions of recoil tritium atoms with mixtures of benzene hexane cyclohexane and perdeuterocyclohexane were showed that substitution was three times more probable at an aromatic than at an aliphatic site. Tritium decay can also produce chemical effects. A theoretical investigation of such decay in the hydrofluoric acid methylamine complex has shown'96 that the 3He atom is ejected immediately and that the complex is disrupted. In solid palladium tritide bubbles of helium-3 under high pressure can form and a solid-liquid phase transition can be detected by NMR at 250 K.'97 "C.-The reactions of carbon-11 atoms (or ions) made by a variety of different nuclear reactions have been in gaseous and solid mixtures of water- ammonia water-methane and ammonia-methane with a view to simulating the primary reactions of carbon atoms from the Sun and cosmic 'rays' in comets and in the upper atmosphere.187 M. G. Noto R. A. Amor D. A. Caviglia M. T. Ratner A. M. Schroder J. C. Rocco and A. C. Mancini ref. 155 p. 184. 1nn J. S. Blais and W. D. Marshall Appl. Radiat. Isot. 1988 39 1259. 189 C. Yi J. Jin and S. Zhang J. Isot. 1988 1 15. 190 K. S. Venkateswarlu Proc. Indian Natl. Sci. Acad. Part A, 1988 54 798. 191 K. Berei L. Vasaros and I.Kiss Kern Koezl. 1988 68 22. 192 (a)T. V. Tsetskhladze L. I. Cherkezishvili and N. Ya. Tsibakhashvili Zh. Fiz. Khim. 1988 62 1690; (b) M. Saeki and N. M. Masaki Radiochim. Acra. 1989 46 163. V. A. Barnov K. Sh. Bobokhidze L. Sh. Nadirashvili and T. V. Tsetskhladze At. Ehnerg. 1988,64,441. G. Izawa K. Shirahashi Y. Murano and K. Yoshihara Radiochim. Acta. 1989 46 191. 193 194 19s K. Oohashi J. Radioanal. Nucl. Chem. Lett. 1988 128 181. 196 Z. Zhu H. Zhao and D. Wang Acta Sci. Nat. Uniu. Pekin. 1988 24 411. 197 G. C. Abell and A. Attalla Fusion Technol. 1988 14 643. 19* B. Nebeling Thesis Cologne University (Chemistry Dept. Nuclearchemistry) Cologne Germany (BRD) 1988; also Report -2245 Kernforschungsanlage Julich GmBH Germany (BRD) 1988.Radiochemistry 129 13 N.-When recoil nitrogen-13 atoms react with materials such as propionic acid labelled ammonia and nitrogen acids are formed.'99 The relative yields of these products are as might be expected from previous work with recoil nitrogen greatly influenced by radiation effects. The yields are also affected by the phase of the reactant as radical reactions can proceed more quickly in the liquid than in the solid. 32 P.-Recoil phosphorus reacts with mixtures of carbon tetrachloride-tetramethyl compounds X(CH3)4 with X = Si Ge Sn and Pb to give labelled methylphos- phonic and mono- di- and tri- chloromethylphosphonic acids;200 in carbon disul- phide-alkanol mixtures labelled 0,O-dialkyldithiophosphates are formed.201 36 C1.-The (n,y) reaction in chloro-compounds generates recoil 3xCl.In bromotri- chloromethane 46% of the radioactive chlorine is found202 in organic combination a figure unaffected by iodine scavenger. The same effect was observed in ortho-and para-chloromethylfluorobenzenes. Iodine was effective however in reducing organic yields in the ortho-and para-trifluoromethylchlorobenzenes.203Relative reactivities of different molecules were evaluated from mixtures using the Kontis- Urch model. Transition Metals.-Mishra and Singh204 have suggested a mechanism for the reac- tion of 56Mn with permanganate and related ions which has provoked2" criticism. In iron phthalocyanine recoil manganese gives up to 6% labelled complex if the reaction is carried out in the solid phase but 0% in solution.206 When potassium chromate is irradiated with neutrons recoil "Cr is produced.The chromium atoms come to rest in a variety of valence states which depend upon chemical environment temperature radiation damage etc. In a recent experiment to determine the 'original' distribution of valence states a mixture of magnesium oxide and potassium chromate was the idea being that Cr"' would be both absorbed and not oxidized on the magnesium oxide. A two fold increase in the amount of trivalent chromium was observed indicating that most recoil chromium is trivalent at first. A much more direct way of studying the initial valence state of an atom in a solid matrix is to use if possible Mossbauer spectroscopy. This has been done for s7Fe produced by electron capture from 57C0 in K[CoF3] and K[NiF3];208 evidence is found for the stabilization of Fe"'.In [57Co]cobalt( 11) iodate the Fe" :FeIrr ratio was found209 to be 0.47.The same method has been used2" to study the fate of 57Fe on ion-exchange materials and zirconium phosphide. Neutron irradiation of ferrocene gives a high yield of labelled parent compound.211 Upon dilution this falls to almost zero 199 Y. Sensui and K. Tomura J. Radioanal. Nucl. Chern. Lett. 1988 128 359. 200 A. N. Bogushevskij and N. I. Lebedev Radiokhirniya 1988 30 567. 201 A. M. Makarov G. K. Genkina and T. A. Mastryukova Sou. Radiochem. 1988 30 267. 202 N. Chandrasekhar and B. S. M. Rao ref. 162 p. 210. 203 N. Chandrasekhar and B.S. M. Rao Radiochirn. Acta 1989 46 25. 204 S. P. Mishra and J. Singh Indian J. Chern. Sect. A 1988 27 192. 205 H. Mueller J. Radioanal. Nucl. Chern. Lett. 1988 127 219. 206 P. Benzi M. Castiglioni and P. Volpe Radiochirn. Acta 1989 46 29. 207 J. M. Lo C. L. Tseng and S. J. Yeh J. Radioanal. Nucl. Chern. 1988 123 683. 208 M. Devillers J. Ladriere and D. Apers Radiochirn. Acra 1989 46 197. 209 Y. Watanabe K. Endo and H. Sano Bull. Chern. SOC.Jpn. 1988 61 2785. 210 I. E. Alekseev and S. I. Bondarevskii High Energy Chern. 1988 22 233. 21 1 R. Blackburn and T. Yassine Radiat. Phys. Chern. 1989 33 337. reaction. Recoil 59Fe behaves differently in phthalocyanine complexes where a 12% retention is observed206 in the solid and a remarkable 6% in solution.The chemistry of recoil 6oCoin metal complexes has been reviewed'" and a new kinetic theory analogous to that for solid state decomposition reactions advanced2I2 to rationalize annealing reactions involving this atom. A detailed study has been made213of the reactions of recoil 6oCo with the tris(acety1acetonato) cobalt( 111) complex when adsorbed onto alumina. Substrate pore size plays a critical role in determining the nature of the labelled compounds. The chemistry of recoil copper atoms produced by the (n y) reaction in N-benzoyl- N-phenylhydroxylaminate and related complexes has been studied.214 Bromine.-The isomeric decay of 82mBr leads to the formation of an excited 82Br species. Detailed investigations have been made215 using solutions of bromomethane 1-bromobutane and 5-bromouridine to determine the nature and origin of this excitation.The results did not support the idea of an Auger induced 'Coulombic explosion' but suggested direct ionization and charge neutralization. The importance of the concomitant y dose has also been indicated216 by a series of experiments using different excitation sources. When recoil 80m Br reacts with bromotri-chloromethane nearly half of the radioactive bromine is found202 in organic combi- nation. Ruthenium.-The various isotopes of ruthenium produced by neutron irradiation have different recoil properties. These give rise to different 'parent yields' when ruthenocene is irradiated with ne~trons.~~Ru in particular undergoes internal conver- sion which initiates Auger ionization.The high yields of labelled ruthenocene which are observed even upon dilution may be explained2l1 by y cancellation and recoil absorption by the lattice. Further experiments with mixed metallocenes indicated217 that ion-molecule reactions play an important role in determining the final fate of the recoil atom. Tellurium.-As is so often observed in hot atom chemistry the matrix plays a dominant role in determining the mix of valence states observed218 for tellurium produced by spontaneous fission of 252Cf. The same effect is found when studying the chemistry of '27Te produced by the isomeric transition reaction. In this case the distribution of Te'" and Te"' was found to be solvent de~endent.~'~ Osmium.-Neutron irradiation of osmocene produces only small yields of labelled osmocene2'1 and even these are reduced upon dilution.As with the related metal- locenes it is proposed217 that the recoil chemistry can be understood in terms of ion-molecule reactions. 212 V. Ramshesh Nut1 Acad. Sci. Lett. 1987 10 429. 213 Y. Sakai A. Kageyama H. Nishioji and T. Tominaga Radiochim. Acta 1989 46 73. 214 C. Nakanishi Thesis Institute de Pesquisas Energeticas e Nucleares Sao Paulo SP Brazil 1987. 215 A. Ebrahim R. J. Meyer and E. P. Rack Radiochim. Acta 1989 46 65. 216 V. G. Dedgaonkar and R. S. Lokhande ref. 162 p. 201. 217 T. Yassine and R. Blackburn Radiat. Phys. Chem. 1989 33 341. 218 Z. Qi P. Zhang F. Wang and J. Guo J. Radioanal. Nucl. Chem.1988 125 271. 219 S. I. Bondarevskij and S. A. Timofeev Radiokhimiya 1988 30,803. Radiochemistry 5 Radiochemistry and the Environment The growing use of radioisotopes and of techniques based on nuclear reactions has led to an increasing concern with the impact of radioactive substances on the environment. This concern is manifest in many ways but the underlying desire is the reduction in exposure to radiation. Techniques are therefore being actively sought to remove radioactive substances from the environment and to ensure that they can be contained safely until their radioactivity is ‘negligible’. An alternative philosophy is that of rapid and extensive dilution and dispersion. (But is the world ready for ‘ban K-40’ and ‘C-14 out’ surely logical successors to the ‘Nuclear Power -No thanks’ and ‘Ban the Bomb’ campaigns).As is so often the case what is suitable for one isotope bearing in mind its nuclear and chemical characteristics global distribution total amount and rate of production will not be suitable for another. Much of the work to be reviewed here concerns the development of methods for removing specific isotopes and their subsequent immobilization (well thats the aim anyway). Two patents have recently been taken out for the removal of heavy metal ions using either a bacterially generated complexing agent220 or an insoluble carboxylated cellulose221 which would both sequester and chelate the ions. The behaviour of actinide ions in mineral waters has been extensively investigated covering topics such as complex formation by americium ions including complexes with humic acid,222 the hydrolysis of americium ions223 and the effect of radiolysis on the solution chemistry of plutonium.224 The removal of actinide ions from solution has also been investigated particular attention being paid to the adsorption onto calcite and related onto alumina,226 and also bentonite,227 as well as the effect that pH would have when granite228 was the substrate.The extent to which actinide ions can be ‘fixed’ in solids such as cement has been investigated,229 related research has measured the mobility of neptunium ions230 in glasses and ceramics. Similar investigations have been made for many lighter radioactive isotopes now being loosed into the environment as a result of the increased use of fission nuclear reactors for power generation.Recent papers have investigated the adsorption of many elements from aqueous solution of europium cobalt and caesium by fresh water sediment^,^^' of antimony(v) onto oxide and hydroxide surfaces,232 of 220 E. T. Premuzic US Patent document 4 780 238/A/ Washington DC USA 1988. 22 1 G. S. Elfine US Patent document 4 764 281/A/ Washington DC USA 1988. 222 (a) V. Moulin P. Robouch P. Vitorge and B. Allard Radiochim. Acta. 1988,44/45 33; (b) J. I. Kim G. Buckau and R. Klenze Report 01 788 Inst. fur Radiochemie der Technische Universitat Munich Germany (BRD) 1989. 223 S. Stadler and J. I. Kim Radiochim. Acta 1988 44/45 39. 224 K. Bueppelmann J.I. Kim and C. Lierse Radiochim. Acta. 1988 44/45 65. 225 T. C. Maiti M. R. Smith and J. C. Lad Radioact. Waste Manage. Nucl. Fuel Cycle 1989 11 269. 226 L. Righetto B. Marcandalli and I. R. Bellobono Radiochirn. Acta 1988 44/45 73. 227 B. Christiansen and B. Torstenfelt Radiochim. Acta 1988 44/45 219. 228 B. Torstenfelt R. S. Rundberg and A. J. Mitchell Radiochim. Acta 1988 44/45 111. 229 H. P. Thomason Report RW-88.094 Department of the Environment London UK 1988. 230 I. A. Ivanov A. N. Gulin V. M. Shatkov and E. A. Shashukov Radiokhimiya 1988 30,817. 23 1 S. M. Khalifa A. A. Halal H. F. Aly and A. M. El-Atrash Isotopenpraxis 1989 25 335. 232 S. Ambe Radiochim. Acta 1989 46 145. 132 D. S. Urch strontium and caesium by zeolites:33 and of fission fragment ions by silver iodide lanthanum oxalate and calcium and barium ~ulphate.~~~ Some ions of this type (cobalt and europium)235 form complexes with the simple organic ligands found in ground water whilst caesium [134Cs]and cobalt [“Co] coprecipitate with nickel(I1) hexacyanocobaltate( 111) thus facilitating their removal from solution.236 The mobility of nickel strontium iodine and caesium ions in bentonite has been studied as a function of pH.227 Other elements such as techenti~m~~~ pose by virtue of their wide range of possible valences greater complications when their water borne migration through rock formations is considered.Yet another aspect of the presence of radioactive materials adsorbed onto or chemically incorporated into minerals which should be considered is their behaviour upon fusion.The volatility of caesium and strontium from basalt as a function of temperature has been studied recently.238 Tritium poses special problems. Attempts to localize it as water of hydration in cements239 have failed (surprise?) but adsorption on iron based alloys has met with greater success.24o The oxidation of tritiated hydrogen to [3H]water has been investigated both in soils (reducing agents lower the rate of conversion to 3HHO)241 and in the gas phase,242 where UV irradiation increases the rate. Similar special environmental problems are associated with radioactive iodine (usually I3’I). For the most part this isotope will be airborne; methods have been developed to limit its release into the atmosphere based on adsorption on active or zeolite.244 The transport of radioiodine is determined by the extent to which it is adsorbed onto colloid particles in the air245 and its partition between the gas phase and The final chemical form (iodide or iodate) in which it is found depends greatly upon chemical especially pH (iodate in the sea and in tap water -iodide in rain and milk).The chemical and physical processes peculiar to radon that affect its interaction with biological systems have been reviewed;248 a complimentary piece of research has considered249 the fate of the daughter element polonium. 233 H. Mimura K. Akiba and I. Yamagishi Nippon Kagaku Kaishi 1989(3) p. 621. 234 M. Csaijka J. Radioanal.Nucl. Chern. 1988 122 333. 23s B. Skytte Jensen and H. Jensen Radiochirn. Acta 1988 44/45 45. 236 F. M. Mekhail K. Benyamin and K. Shakir Radioacf. Wasre Manage. Nucl. Fuel Cycle 1989 11 279. 237 T. Kanno Nippon Genshiryoku Gakkai-Shi 1988,30 313. 238 C. W. Sill Nucl. Chern. Waste Manage. 1988 8 97. 239 K. Nishimaki and T. Tsutsui Hoken Butsuri 1989 24 3. 240 M. Matsuyama K. Ashida H. Miyake K. Watanabe and Y. Araki Toyarna Daigaku Torichurnu Kagaku Senta Kenkyu Hokoku 1989 8 41. 24 1 M. Ichimasa Y. Ichimasa Y. Azuma M. Komuro K. Fujita and Y.Akita J. Radiat. Res. 1988,29 144. 242 S. Usami Y. Asai K. Hasegawa M. Matsuyama K. Watanabe and T. Takeuchi Toyarna Daigaku Torichurnu Kagaku Senta Kenkyu Hokoku 1989 8 75. 243 (a)W. P. Freeman M.P. King and J. L. Kovach ‘Proceedings 19th DOE/NRC Nuclear Air Cleaning Conference’ USDOE Assnt. Sec. for Environment Safety and Health (Nuclear Regulatory Comm.) Washington DC USA 1987 p. 237; (6) V. R. Deitz ibid. p. 265; (c) D. J. Gladden and M. Post ibid. p. 288; (d) H. G. Dillmann and H. Pasler ibid. p. 278. 244 Y. C. Fan T. Y. Lee C. S. Tan and C. M. Hsai ibid. p. 136. 245 H. Noguchi M. Murata and H. Matsui Proc. 7th Congress of the International Radiation Protection Association Australian Radiation Protection Society and Pergamon Press Sydney Australia 1988 p. 702. 246 G. J. Evans R. E. Jervis and E. G. Csillag J. Radioanal. Nucl. Chern. 1988 124 145. 241 Y. Muramatsu and Y. Ohmomo J. Radioanal. Nucl. Chern. 1988 124 123. 248 A.W. Castleman Jr. Report ER/60 668-1. Department of the Environment Washington DC USA 1988. 249 C. R. Phillips ref. 245 p. 894. Radiochemistry 6 Miscellaneous Detection.-An elegant new method has been developed for measuring the radio- activity that might be present in a minute droplet.250 The technique has been specifically developed for 14C labelled species. An electric field acts upon the charge the drop aquires as a result of radioactive decay just enough to counteract the force of gravity. In this way activities as low as 3 Bq have been detected. Simplified procedures have been reported for the analysis of high resolution y spectra from germanium detectors.251 The general problems of random and systematic errors and what is meant by the ‘minimum detectable amount’ of radioactivity have been considered252 and an improved geometry for the detection of a radiation has been developed.253 The kinetic and thermodynamic problems associated with assemblies of only a very few atoms have been considered254 and modifications to the laws of mass action etc.proposed based not on concentrations but the probability of finding a particular species in a given state and in a given phase. The detection of impurities in radiopharmaceuticals is of great concern as well as the accurate determination of the radioactivity of any particular preparation. Recent examples of these problems are to be found in papers dealing with the measurement of free 13’1 in labelled i~dohippuran~~~ and in or i~doamphetamin~~~ the determination of the specific activities of 1251 labelled thyroxine^,^^' or pertech- nate.258 The level of impurity associated with pertechnate anions produced from generator is also quite rightly of continuing concern.The storage of labelled compounds always poses problems due to autoradiolysis which will compromise radiochemical purity. The effects due to storage of adenosine triphosphate for many months have been studied259 and it is claimed that activities up to 400 GBq (thats about one tritium atom per molecule) can be kept in a ‘reasonably satisfactory’ state for more than a year! Spectroscopy.-When y radiation is internally converted the energy is utilized in the ejection of an electron. Depending upon the valence state and local environment of the atom in which this process occurs so will the kinetic energy of the electron be effected as is well established from photoelectron spectroscopy.Internal conver- sion electron spectroscopy can therefore be used with elements such as techentium260 to determine directly the valence state of an emitting atom. Resonance Raman 250 T. L. Ward E. J. Davis R. W. Jenkins Jr. and D. D. McRae Rev. Sci. Instrum. 1989 60,414. 25 1 H. B. Spitz R. Buschbom G. A. Rieksts and H. E. Palmer ‘Proceedings of 30th Annual Conference on Bioassay and Environmental Chemistry’. Pub NLO Inc. Cincinnati Ohio USA 1985. 252 A. Brodsky ibid. 253 D. Mascanzoni J. Radioanal. Nucl. Chem. 1988 124 431. 254 R. Guillaumont J. P. Adloff and A. Peneloux Radiochim.Acta 1989 46 169. 255 D. K. Ranganatha P. D. Soman and R. S. Mani ref. 162 p. 380. 256 A. Hammermaier T. Reichert E. Reich and K. W. Boegl Nuc. Compact 1988 19 113. 257 D. Ji and Y. He J. Nucl. Radiochem. 1988 10 36. 258 J. Silar and F. Budsky Jad Energ. 1988 34 290. 259 R. Lakshmi D. Padmanabhan A. U. Garana and K. V. Viswanathan ref. 162 p. 148. 260 (a) M. Fiser V. Brabec 0. Dragoun A. Kovalik M. Rysavy and N. Dragounova AppZ. Radiat. Zsot. 1988 39,943; (b) M. Fiser 0. Dragoun V. Brabec A. Kovalik M. Rysavy U. Mazzi A. Moresco F. Refosco and F. Tisato ref. 150(b) p. 57; (c) 0. Dragoun M. Fiser V. Brabec A. Kovalik A. Kuklik and P. Mikusik Czech. Patent 243 954/B1/ Prague Czechoslovakia 1988. 134 D. S. Urch spectroscopy has also been used261 to study technetium complexes.Tritium labelled compounds can be studied using tritium NMR,262 and the location of the tritium atom established. Applications.-Radioactive 1-iodohexane has been used to label tar from cigarettes (they were doped).263 This enabled the tar in the ‘mainstream’ smoke to be measured on a puff-by-puff basis! Muon Chemistry.-The capture of negative muons by organic molecules has been investigated.264 It was found that whilst the probability of capture was roughly proportional to the atomic number of the atom there were small variations which could be rationalized by ab initio molecular orbital calculations for the individual molecules. 261 A. Davison R. M. Pearlstein P. A. Mabrouk A. G. Jones and M. M. Morelock ref.150(b) p. 25. 262 (a)P. G. Williams Fusion Technol. 1988 14 840; (b) L. Zhang and J. R. Jones J. Isot. 1988 1 28. 263 J. N. Pritchard J. J. McAughey and A. Black J. Aerosol Sci.,1988 19 715. 264 M. K. Kubo Y. Sakai T. Tominaga and K. Nagamine Radiochim. Acta 1989,47 77.

ISSN:0260-1818    

DOI:10.1039/IC9898600117

出版商:RSC    

年代:1989

数据来源: RSC

摘要:

Abad J.A. 19 Abbar-Ah M. 66 Abdel-Fattah H.M. 98 Abdul-Dayem H. 125 Abdulla A.I. 112 Abel E.W. 31 Abell G.C. 128 Abney K.D. 109 Abrahams B.F. 69 Abram U. 126 Abrams D.N. 127 Abriel W. 47 41 Abu-Ragabah A. 65 Acampora L.A. 44 Ache H.J. 119 Adam K.R. 63 68 Adam M.J. 124 124 Adams H. 14 16 64 Adams M.W.W. 31 Adams R.D. 31 Addison A.W. 65 Adham K. 125 Adloff J.P. 133 Agirbas H.A. 72 Aguilar M. 70 71 Ahern D.G. 121 Ahlers F.-P. 41 Ahn B.T. 28 Aho K. 118 Airoldi C. 70 71 113 Aitken C. 113 Ajdinovic B. 126 Akai R. 117 Akashi H. 32 Akiba K. 132 Akita Y. 132 Akitt J.W. 6 7 Akiyoshi K. 69 Al-Awadi S. 125 Albin M. 62 Albinsson Y. 85 Albrecht-Gary A.M.62 Albright T.A. 24 Alcock N.W. 62 63 110 Aleandri L.E. 17 35 42 Alekseev I.E. 129 Alex S. 61 Alexander R.S. 61 Alexoff D. 118 Alfassi Z.B. 118 Mi A.A.M. 32 Ali S.A. 119 Alidoosti M. 59 Alikhanova T.Kh. 89 Aliludin Z. 119 Al Imarah F.J.M. 109 Alivisatos A.P. 68 Al-Juaid S.A. 70 Al-Kouraishi S.H. 126 Allan J.R. 65 Allard B. 131 Allen J. 121 Allen S.R. 31 Allison J. 78 Alper H. 84 Al-Showiman S. 72 Aly H.F. 131 Al-Yanbawi S.J. 119 Alyea E.C. 74 Amarasekera J. 37 Amarilla A. 47 Ambe S. 131 her,I. 84 Amico P. 65 Amma E.L. 67 70 Amodor J. 23 Amor R.A. 128 Andersen R.A. 106 107 Anderson D.G. 27 Anderson D.M. 108 Anderson H.L.64 Anderson J.E. 112 Anderson O.P. 47 62 99 Andratschte M. 48 Andrews L. 49 55 56 Andruszkiewicz R. 14 Ang K.P. 66 Angilella V. 42 Annan T.A. 13 15 17 Ansari M.A. 45 Antolini L. 74 Antoni G. 124 Aoki I. 11 Apblett A, 42 Apers D. 129 Appelman E.A. 57 Appelman E.H. 112 Arai H. 89 Arai T. 16 Araki S. 69 Araki Y. 132 Araullo C. 62 Aravamudan G. 33 Arduengo A.J. 54 Arena G. 67 Arguelles M.G. 126 Arif M. 58 Annentrout P.B. 19 Annitage M.D. 72 Armstrong M.M. 65 Armstrong R.S. 38 Arnold A.P. 74 Arnoud-Neu F. 86 Arsenault G.J. 72 Arugg R. 67 Asai Y. 132 Aschien C. 87 Ashida K. 132 Aspinall H.C. 90 Astier R. 92 Atcher R.W. 120 Atkinson N.26 Attalla A, 128 Atwood J.A. 72 Atzei D. 50 Aubke F. 50 Audiere J.P. 28 Avasthi B.N. 9 Avens L.R. 109 Avent A.G. 78 Averbuch-Pouchot M.T. 68 Avsar E. 66 Awaluddin A. 126 Awere E.G. 41 Axup A. 62 Ayame A. 8 Azeez W.I. 112 Azran J. 121 Azuma Y. 132 Babcock G.T. 62 Babecki R. 110 Ba Chauh N. 47 Badawy S.S. 98 Bader R.F.W. 53 Baenziger N.C. 70 Baglio J. 39 Baidoo K.E. 127 Bailey N.A. 14 16 64 Bailey T.D. 40 69 135 Baisden P.A. 86 Bakac A. 28 Bakr S.A. 127 Balakrishnan S.A. 126 Balatoni J.A. 124 Balch A.L. 75 Baldass J. 126 Baldus M.P. 42 Baltina L.A. 125 Banci L. 61 Bandoli G. 126 Banister A.J. 26 Bank S.68 Banks P.M. 35 Bankston C.P. 5 Bannister R.M. 26 Bannyman J. 126 Bao Y. 121 Baohu D. 104 Baral S. 68 Barbe J.M. 62 Barbier J. 13 Bardan M. 51 Barluenga J. 71 Barnfield E.A. 29 Barnov V.A. 128 Barrio J.R. 124 Barron A.R. 11 12 Barry J.P. 113 Barta C. 71 Barthelemy P.P. 88 Bartik T. 63 Bartlett N. 53 54 58 Barton R.J. 65 Bastide J.-P. 47 Bastos M.A.V. 118 Bates P.A. 58 Battaglia L.P.,67 Battistuzzi-Gavioli G. 67 Bautista F.M. 11 Bayense C.R. 13 Bayer A.G. 123 Beattie J.K. 38 Beauchamp A.L. 75 Beaucourt J.P. 121 122 Beaudoin R. 71 Beauvy M. 77 Becher J. 30 Bechgaard K. 43 Beck J.L. 62 Bedia Erim F. 66 Beeley N.R.A. 17 78 Beger J.66 Behm H.J. 65 Behrens P. 59 Bein T. 29 40 46 68 Bekkum H. 85 Belaud C. 63 Beletskaya I.P. 88 Belin C. 42 Belkalem M. 112 Bell M. 63 Bell N. 65 Bell N.A. 65 66 74 Author Index Bell P. 75 Blackburn R. 129 130 Bell T.W. 68 Blackburn T.R. 6 Bellito C. 39 Blais J.S. 128 Bellobono I.R. 131 Blake A.J. 26 75 Belloma J.M. 87 Blancou H. 63 Bellus D. 63 Blasse G. 87 Bel’sky V.K. 63 Blatov V.A. 109 Benac B.L. 69 Blaufox M.D. 126 Benazeth S. 14 42 Block E. 69 Bencini A. 62 64 67 Blok D. 126 Benedetti A. 74 Blomqvist G. 123 Benelli C. 81 85 95 Bobin J.E. 31 Benetollo F. 100 101 102 Bobokhidze K.Sh. 128 Bengtsson L. 74 Bocarsly A.B. 88 Benning M.M. 111 Boegl K.W. 119 133 Beno M.A.47 Boehm H.P. 58 Benyamin K. 132 Boehmer R.G. 118 Benzi P. 129 Boere R.T. 27 Bercaw J.E. 79 Boersma J. 63 Berei K. 128 Boeshagen H. 123 Berg D.J. 106 Bogdanova V. 126 Berg R.W. 6 Bogge H. 31 Bergman J. 118 Boggs J.E. 29 Bergman R.G. 35 53 Bogushevskij A.N. 129 Berlitz T.F. 71 Bohn R.B.,55 56 Berno P. 31 Bojeson G. 30 Berolasi V. 74 Bolomey L. 118 Berridge M.S. 118 Bombi G.G. 11 Berry M.T. 87 Bombieri G. 100 101 102 Berstresser G.L. 63 Bonamartini-Corradi A. 67 Bertani R. 65 Bonamico M. 39 Bertini I. 61 Bonasera T.A. 125 Besida J. 50 Bond A.M. 69 72 Bespalova S.D. 121 Bondarevskii S.I. 129 130 Besselievre R. 121 Bonds A.M. 47 Best S.P. 38 Boniface G.R. 127 Bestari K.T. 27 Bonoma R.P. 65 Bettinelli M.87 Bonomo R. 67 Bettonville S. 113 Booij M. 104 Beydoun N. 39 Booiu M. 103 Beyer L.,75 Borovik AS. 62 Beyermann M. 121 Borsari M. 67 Bharadwaj S.R. 48 Botlogg B. 21 Bhargava K.K. 126 Bott S.G. 72 112 Bhatia S.C. 49 72 Bot:ari E. 67 Bhattacharjee C.B. 109 1 Bottino F.A. 66 67 Bhattacharya S. 46 Boudin C. 11 1 Bianchi A. 62 67 Boudjema B. 63 Bidoglio G. 11 1 Boulard B. 3 Bielski R. 75 Bourell J. 122 Bienert M. 121 Bourgault D. 19 Biggs D.B. 21 Bowley H.J. 65 Bigoli F. 50 Boyce B.A. 17 78 Bijma A.T. 124 Brabec V. 133 Bilgin M. 40 Bradley D.C. 78 90 Bill E. 31 Brady F. 124 125 Bingler L.S. 86 Brainard J.R. 78 Birchall T. 51 Braithwaite E.P. 38 Birdsall W.J. 66 Braun U. 74 Birkle S. 12 Breitinger D.K.72 Bismondo A, 109 Brennan J.G. 64 68 Bjerrum N.J. 6 Bretey E. 40 Blachnik R. 42 Brianese N. 113 Black A. 134 Briggs B.D. 80 Author Index Brihaye C. 120 Brinckman F.E. 87 Brinkman G.A. 118 Brisse F. 16 Brits R.J.N. 118 Brodsky A. 133 Brova J. 67 Brown M.P. 66 Brown P. 29 Brown P.L. 13 Brown R.D. 86 Brown S.H. 72 Bruce D.W. 64 Brucher E. 12 Bruchertseifer H. 120 Bruck M.A. 113 Bruechle W. 120 Brun G. 47 Brundish D.E. 121 Bruni S. 65 Bruno A. 47 Brus L.E. 68 Buchler J.W. 86 101 Buchman O. 121 Buckau G. 131 Budnikova U.I. 89 Budsky F. 119 133 Budzelaar P.H.M. 63 Bunzli J.C.G. 86 Bueppelmann K. 131 Buerck J. 119 Buerskens P.T.65 Buhro W.E. 80 Bulbulian S. 118 Bulgakov R.G. 88 Bulychev B.M. 63 Burckhardt W. 15 Burford N. 28 29 Burg A.B. 28 Burlitch J.M. 65 Bums C.J. 107 113 Bums H.D. 127 Burns J.C. 78 Bums S.J. 106 Burshtein K.Y. 72 Bursten B.E. 32 78 113 Burtlitch J.M. 74 Burton D.J. 70 Burton M.C. 79 Buschbom R. 133 Butcher K.D. 64 Butsugan Y. 69 Buttrus N.H. 70 Byrne R.H. 86 Cader M.S.R. 50 Cai W. 74 Caignaert V. 23 Calahorra Z. 16 Calhoun C.S. 23 Callahan A.P. 120 Calo R.,65 Calomer J. 71 Calvo R. 61 Cambon O. 11 Cameron T.S. 28 Campelo J.M. 11 Canadell E. 18 35 Canellas C.O. 126 Caneschi A. 95 Cao G. 69 Cao Y. 49 Cardin R.L. 81 Cariato F.65 Carlsson P. 15 Carney M.J. 30 31 Carpenter G.B. 28 Carre D. 16 Carrie Faget C. 127 Carroll P.G. 68 Carron B. 65 Carugo O. 88 Casaba J. 65 71 Casas I. 70 Casas J.S. 19 67 72 Casassas E. 66 Cascales C. 23 Casellato U. 90 Cassidy J.M. 20 Castano M.V. 72 Castella M. 67 Castellano E.E. 67 72 Castelloni C.B. 88 Castiglioni M. 129 Castillo J. 72 Castleman A.W. jun. 132 Castner D.G. 75 Castro A. 48 Caulton K.G. 91 92 Cava R.J. 21 Caviglia D.A. 128 Cayetano C.J. 127 Cerny B. 127 Chaabouni M. 57 Chadha R.J. 17 Chagas A.P. 70 71 113 Challen P. 68 Chamberland D. 16 Chan W.H. 18 Chandrasekhar N. 129 Chang C.T. 80 Chang X. 127 Charewitz W.66 Charles R.G. 22 Charnock J.M. 30 Chary K.V.R. 8 Chattopadhyay G. 48 Chau C.-N. 45 Chaudhuri M.K. 109 Chauvin Y.,83 Cheesman B.V. 74 Cheetham A.K. 10 Chen X. 83 Chen Z. 83 85 Chenevert R. 16 Cheng S. 7 Cherkezishvili L.I. 128 Chermette H. 63 Chervu L.R. 126 126 Chessa G. 74 Chevrel R. 35 Chien D.H.T. 121 Chiesi-Villa A. 31 Chirakal R. 124 Chivers T. 26 42 Chniber T. 70 Choe W.-Y. 21 Choi Q.W. 21 Choisnet J. 48 Chopin G.R. 112 Choppin G.R. 88 Chou M.H. 61 Choudhari S.T. 83 Choudhary V.R. 11 83 Choy J.H. 80 Choy R.-H. 21 Christe KO. 49 50 52 58 Christiansen B. 131 Christianson D.W. 61 Chudley N.A. 74 Chun S.B. 126 Churchill M.R.62 Cian A.D. 101 Ciani G. 65 Ciavatta L. 85 Cicinotta V. 65 Ciliax B.J. 125 Ciurli S. 31 Clark D.L. 112 Clayden N.J. 35 Clayton R.H. 32 Clearfield A. 65 Clegg W. 26 64 Clemenson P.I. 38 Clement R. 28 Clevette D.J. 12 Cloke F.G.N. 79 108 Coan P.S. 92 Cocivera M. 68 Coenen H.H. 124 Coetzee P.P. 120 Cohen S.L. 64 Cohn K.C. 113 Collins C.H. 118 Collins J.D. 71 Collins K.E. 118 Colton R. 39 69 72 Commeyras A. 63 Conder K. 22 Coneschi A, 81 85 Cong-Ngoan D. 95 Constable E.C. 72 Cook R.L. 17 112 Cooper E.I. 23 Cooper G. 122 Coppo M. 122 Corain B. 11 Corbeil M.-C. 75 Corbett J.D. 81 82 Cordes A.W. 27 Cormack A.N. 9 Coronado P.R.121 Cortes M.E. 127 Cortneidge J.L. 72 Corwin D.T. 61 Cosellato IJ. 113 Cossery J.M. 122 Cossio F.P. 65 Cossy C. 85 Cotton F.A. 24 32 35 Coucouvanis D. 32 68 Counsell R.E. 123 Courbion G. 4 6 12 Cowan J.A. 45 Cowley A.H. 69 Cox D.E. 40 68 Cox J.P.L. 78 Cox P.A. 108 Crabtree R.H. 72 Craig A.S. 14 16 17 Craig D.C. 40 66 69 Cramer R.E. 113 114 Crawford M.K. 24 Cristini P.R. 119 Crouch A.M. 62 Crouzel C. 123 125 Crutchley R.J. 62 Csaijka M. 132 Csillag E.G. 132 Csoregh I. 91 98 Cucinotta V. 67 Cudennec Y. 20 Cumbrera F.L. 43 Cusick J. 66 Cybulski Z. 47 48 Cyr M. 68 Czeka C.L. 64 Czernuszewicz R.S. 31 Czugler M. 98 Dagnall S.P.65 Dakternieks D. 47 69 Dalas E. 68 Dancay K.P. 68 Dance I.G. 40 66 69 Daniele P.G. 65 67 Danks I.P. 99 Dannals R.F. 123 Dapporto P. 62 Dargetz M. 63 Das M.K. 119 da Silva A.G. 118 da Silva C.P.G. 119 da Silva R.F. 118 Davidson J.L. 18 Davies A.G. 72 Davies G. 65 Davies P.K. 23 Davis E.J. 133 Davis S.R. 56 Davison A. 134 Davolos M.R. 14 Dawod M.M. 99 Day P. 80 Day V.W. 24 Deacon G.B. 72 94 105 107 Deakin M.R. 7 Deakyne C.A. 53 Dean P.A.W. 48 69 72 de Britto J.L.Q. 118 Decock-Le-Reverend B. 61 DeCola L. 100 102 Dedgaonkar V.G. 130 De Graff R.A.G. 71 De Gregori I. 126 de Grout R.A. 23 de Haan J.W. 13 Deiseroth H.-J. 75 Deitz V.R. 132 DeJersey J.62 de Leenheer A. 123 De Leeuw D.M. 24 de Lemos H.C. 79 delevie R. 75 Delpeuch J.-J. 70 Demas J.N. 87 Deming T.J. 92 95 103 Dence C.S. 125 Denis A. 125 Dent Glasser L.S. 9 DeNuzzio J.D. 8 dePaula J.C. 62 Deplano P. 50 Deschamps J. 121 Descroix J.P. 6 de Silva M.L.C.P. 70 Desseyn H.O. 74 Detsellier C. 85 Dettman H. 85 Deutsch E. 126 Devi G.S. 110 Devillers M. 129 Dewar M.J.S. 74 Dewez S. 120 Dexpert H. 42 Dhathathreyan K.S. 26 Dhillon R. 64 Dhingra S. 17 42 Diamondis E.P. 88 Dias A.R. 113 DiCasa M. 126 Didzuilis S.V. 64 Dietrich A. 107 108 Dietrich-Buchecker C. 62 68 Dietzsch W. 17 Di Giacomo R. 47 Dijksman J.A.R. 124 Dilimann H.G.132 Dillon K.B. 51 Ding R. 121 Ding S. 122 123 Di Vairi M. 67 Dixon D.A. 54 Dixon K.W. 30 Djokic D. 126 Dmitriev P.P. 119 Dobbs K.D. 29 Doerge D.R. 125 Doi L. 106 Dokkycz S.J. 64 Author Index Dollase W.A. 11 Domen K. 16 80 Dong S. 17 Doran J.C. 92 Dorhout P.K. 109 Dormond A. 112 Douglass D.C. 68 Downey S. 118 119 Downs A.J. 29 57 Dragoun O. 133 Dragounova N. 133 Dresselhaus M.S. 59 Drew M.G.B. 26 Drewes R.M. 3 Driessen W.L. 67 Driss A. 10 Droznik R.R. 120 Druliner J.D. 21 Drummond D.K. 107 Duatti A. 126 Dubler E. 61 67 du Bois A. 47 Dubois P. 25 Dubois R.H. 4 Ducummon Y. 65 85 Duesler E.N. 18 Duffy N.V. 17 Dugue J.37 Dukat W. 70 Dumas J.F. 47 Duiiach E. 84 Dunaeva K.M. 109 Duncan T.M. 68 Dunmur D.A. 64 Dupont J. 39 DuPreez J.G.H. 109 Dupuis P. 67 Dwight K. 39 Eaborn C. 70 72 Eaton M.A. 17 Eaton M.W. 78 Ebner J. 39 69 72 Ebrahim A. 130 Echigoya E. 8 Eckert H. 42 Eddy M.M. 40 46 68 Edelman F.T. 107 Edelman M.A. 78 Edelmann F. 113 Edelmann F.T. 18 Edelstein N. 108 Edge S. 30 Edgell R.G. 23 Edwards A.J. 63 96 Edwards H.G.M. 72 Edwards P.P. 64 Eggins B.R. 68 Ehkhn L. 120 Ehrenkaufer R.E. 123 Eichler B. 120 Ekstrom A. 83 El Alami N. 63 El-Atrash A.M. 131 Author Index 139 Elbanowski M. 95 Feltz A. 47 48 Fujisawa Y. 124 Elders J.M.6 7 Fendler J.H. 68 Fujita K. 132 Elfine G.S. 131 Feng X. 24 Fujitani T. 8 Elias H. 61 Feng Z. 67 122 Fujiwara N. 110 El-Issa B.D. 32 Fenske D. 45 Fujiwara Y. 83 El Khalifa M.A. 33 35 Ferguson G. 16 Fuksova K. 122 El Khatib N. 63 Fermi F. 87 Fukutomi H. 110 El-Kheli M.N.A. 70 Fernandez H.O. 119 Furnari E.S. 119 Eller P.G. 109 Ferretti V. 74 Furphy B.M. 94 Ellis A.B. 40 68 109 Festa M.R. 67 Furstner A. 64 Ellis P.D. 67 68 Fettinger J.C. 62 Furumo N.C. 12 Ellis S.R. 69 Fiesso J.L.G. 23 Fux P. 11 1 El Mail R. 47 Filer C.N. 121 Elman B.S. 44 Finke R.G. 107 Gai P.L. 21 80 El-Sayed M.A. 65 Finn R.D. 117 125 Gaitan M. 47 El-Toukhy A. 65 Finocchiaro P. 66 88 Gaitonde S. 126 Emsley J. 58 Firnau G. 124 Gaizer F. 62 Endert G. 127 Fischer B. 63 Galesic N.110 Endo K. 129 Fischer J. 101 Cali S. 10 Endo M. 59 Fiser M. 133 Gallagher P.K. 22 Endo T. 47 Fisher K.J. 74 Gallucci J.C. 18 Englert U. 72 Fisman C. 127 Galy J. 94 Eom T.Y. 110 Fjellvag H. 48 Gambardella M. 49 Ephritikhine M. 11 1 Flahaut J. 47 Gang Z. 99 Epstein I.R. 57 Flavell W.R. 23 Ganguli A.K. 24 Erdtmann G. 125 Fleet M.E. 10 Ganja E.A. 72 Ertan A. 91 Fleischer E.B. 63 Ganne M. 18 Ervine J.T.S. 68 Fleming R.M. 21 Gao Y.-M. 28 39 Espenson J.H. 28 Flippen R.B. 24 Garana A.U. 133 Estevez J. 120 Floriani C. 31 Garbay-Jaureguiberry C. 12 1 Esumi K. 8 Florke U. 17 Garbuzov V.M. 120 Ettorre R. 29 Folk P. 125 Garcia A. 11 14 Etzenhouser R.D. 11 1 Folkes S. 102 Garcia R. 65 Eulitz B. 74 Folting K. 91 92 Garcia-Espana E. 62 67 Evain M.18 Fonrodona G. 66 Garcia-Fontan S. 67 Evans D.F. 66 Fontaine X.L.R. 6 7 38 Gardner G.J. 57 Evans G.J. 132 Forsyth C.M. 107 Garner C.D. 30 Evans J. 30 Forsyth G. 26 Garnett E.S. 124 Evans W.J. 81 92 94 95 103 Fouassier C. 14 Gasperin M. 9 106 107 Fourati M. 57 Gatehouse B.M. 10 72 107 Exner J. 122 Fourquet J.L. 3 Gates B.D. 47 Fox J.E. 122 Gatteschi D. 81 85 95 Fabre J.-M. 43 Foxman B.M. 44 Gaudemer A. 63 Fabretti A.C. 74 Frampton C.S. 51 Gauvin F. 113 Facchin G. 65 Franke U. 127 Gbehi T. 9 Fackler J.P. 72 Frankel R.B. 30 Ge Y. 122 Fait J.F. 26 42 Franken K. 124 Gebner W. 9 Faltysek R.A. 87 Freeman W.P. 132 Geboes P. 74 Fan Y.C. 132 Freiser B.S. 30 79 Gedeonov A.D. 119 120 Fanwick P.E. 14 Frenking G. 53 Gee A.D. 123 Fares V.39 Friedman A.M. 120 Geelen G.J.P. 24 Faridoon ,38 Frier M. 121 Geier G. 72 Farnham W.B. 54 Fries K. 62 Geitner M. 103 Farrar D.H. 39 Farrington G.C. 8 Frigeri C. 15 Frigerio A. 69 Gelerinter E. 17 Gellert R.W. 74 Farwaha R. 72 Frohn H.J. 53 Geloso C. 15 Fasth K.J. 124 Fromageot P. 122 Genkina G.K. 129 Faus J. 67 Fronaeus S. 64 Geoffroy G.L. 64 Favarato M. 11 Fronczek F.R. 67 Georgieva R. 126 Fawcett J. 110 Fry A.J. 84 Geraldes C.F.G.C. 86 Fawcett V. 72 Fryzuk M.D. 36 Gerault Y. 20 Fearon E.M. 117 Fuchs J. 50 Gerkin R.E. 18 Feguson G. 38 Fuentes J. 66 Germain P. 47 Feitsma R.I.J. 126 Fujisawa G. 117 Gernon M. 69 Author Index Gerrard D.L. 65 Ghose J. 9 13 Gibbons P.C. 80 Gibson J.M. 68 Giddings S. 83 Gilbert T.M.115 Gildersleeve D.L. 125 Gilje J.W. 113 114 Gill G. 74 Gillard R.D. 64 71 Gisselbrecht J.P. 86 Giusti A, 74 Gladden D.J. 132 Gleizes A. 94 Glenz M. 103 Gleria M. 65 Gobetto R. 74 Goeiji J.J.M. 118 Goel S.C. 80 Goethais P. 123 Goffart J. 113 Gogu E. 30 Goh L.Y. 37 Goiffon A. 11 Golic L. 75 Gonzales-Duarte P. 69 Gonzalez AS. 29 Goodenough J.B. 35 Goodgame D.M.L. 72 90 98 Goodman C.H.L. 22 Goodman M.M. 124 Gopalakrishnan G. 127 Gorbunov A.I. 63 Cord J.R. 79 Gorg S.P. 22 Gorgues A. 43 Gorman A.A. 24 Goryushkin V.F. 80 Could K.L. 118 Gourier D. 9 Gowan J.A. 67 Gowenlock B.G. 72 Graddon D.P. 65 Gradeff P.S. 94 95 Grandjean F. 81 Gratzel M.62 Gray H.B. 45 62 67 Graziani R. 90 113 Greaney M. 37 Green J.C. 108 Green J.F. 124 Green J.H. 15 Green M.A. 125 Greenblatt M. 37 Greitz T. 123 Greiwe K. 68 Grenthe I. 111 Griffith E.A.H. 70 Grimm H. 30 Grimshaw J. 68 Gntzner G. 71 Grondin J. 63 Gross H. 72 74 Gross M. 86 Gross P. 74 Gruehn G. 81 Gruehn R. 75 81 Gruff E.S. 61 Gtowiak T. 95 Guastini C. 31 Guchteneire F. 124 Guddat T. 124 Guilard R. 35 62 112 Guillaume M. 120 Guillaumet G. 122 Guillaumont R. 133 Guillou O. 85 Guiton T.A. 64 Guittard M. 14 16 37 42 Gukathasan R.R. 39 Gulin A.N. 131 Gumrukcuoglu I.E. 63 Guner O.F. 3 Guo J. 130 Gupta N. 70 Guseva L.I.120 Gutierrez M.D. 67 Gutierrez-Jugo J.F. 19 Gyr E. 67 Haaparanta M. 118 Haasbroek F.J. 118 Hadj-Bagheri N. 39 Hadjikyriacou A.I. 32 Haensicke A. 121 Haeuseler H. 27 Hagen K. 65 Hagenmuller P. 14 Hagiwara R. 58 Hague D.N. 65 Hajela S. 74 Hakalahti L. 127 Hake D. 6 83 Halac B. 69 Halal A.A. 131 Halbert T.R. 33 Hall C.D. 99 Hall D.P.J. 64 Hall J.H. 49 Hall L.D. 124 Halldin C. 123 Halperin J. 86 Halsbergen F.B. 71 Hamacher K. 125 Hamblett I. 24 Hamdan H. 7 Hamdi A.H. 7 Hammel A. 103 Hammerle B. 74 Hammermaier A. 133 Hammerschmitt P. 101 Hampden-Smith M.J. 18 Han S. 31 Han Z. 122 Hanafusa T. 3 Hanaki A, 63 68 Hanggi G. 61 Hannibal P.106 Hansford M.I. 26 Hara T. 123 Haradahira T. 125 Harding M.M. 66 Harris D.C. 80 Hams R.K. 28 Harris T.D. 68 Harrison A. 17 78 Harrison J.F. 78 Harrison M.R. 64 Harrison W.T.A. 10 Harrod J.F. 113 Harrofield J.M. 94 Hartikka M. 127 Hasegawa K. 132 Hasegawa T. 23 Hassan M. 125 Hatajima T. 84 Hattiwanger R.C. 63 Haupt H.J. 17 Hauptrnan Z.V. 26 Hausler H.-J. 75 Hawkins W.T. 100 101 Hayashi A, 44,45 He S. 122 He Y. 133 Heeres H.J. 103 105 Hegde M.S. 28 Heineman W.R. 126 Helm L. 85 Helps I.M. 16 17 Hemrni G. 86 Hemon A. 4 6 Hendry P. 63 Henery M. 65 Henkel G. 37 53 Hepler L.G. 69 Herath Banda R.M. 40 66 Herdering W. 124 Herrndorf M.63 Herron N. 29 40 46 68 Herscheid J.D.M. 124 Hervieu M. 19 23 Hichwa R.D. 118 Higgins B.E. 23 Higo M. 7 Hikita T. 38 Hill C.L. 62 Hillier I.H. 53 Hilmes G.L. 87 Hink K. 79 Hinkelmann K. 30 Hinz L. 66 Hirano K. 123 Hirano S. 14 Hirayarna S. 75 Hirose J. 61 Hirose M. 109 Hitchcock P.B. 70 79 94 104 Hjuler H.A. 6 Hocken J. 56 Hodgson K.O. 64 Hofer F. 64 Hoffmann A.J. 127 Author Index Hoffmann R.D. 81 Imamura H. 83 Johannsen B. 126 Hofmann E. 124 Imoto H. 33 John E. 125 Hoge D. 55 Imperatori P. 39 Johnson D.C. 45 Hojo M. 25 Indrasenan P. 110 Johnson E. 65 Holder A.J. 75 Ingleto G. 87 Johnson K.E. 65 Hollamby P.C. 23 Inomata Y. 66 Johnson S. 74 Hollenkamp A.F.47 69 Inoue M. 7 Johnston D. 121 Hollnagel A. 45 Inoue Y. 36 Jones A.G. 134 Holm R.H. 30 31 Inui T. 7 Jones C.J. 96 97 98 Holmberg B. 74 Irish D.E. 66 Jones J.R. 117 134 Holmes S.A. 94 Isaev A.N. 72 Jones K.L. 72 Holmstrom B. 15 Ishiguro S. 69 71 Jones M.M. 67 Holwill C.J. 65 Ishiguro T. 23 Jones M.T. 44 Hondrick K. 106 Ishikawa N. 117 Jones N.L. 24 81 Hong S.T. 80 Islam A.A.M.A. 110 Jones P. 49 Hoppe R. 81 Issa Y.M. 98 Jones P.G. 19 Horowitz H.S. 21 80 Ito H. 69 Jones R. 64 Horvatic D. 110 Ito T. 35 Jones R.A. 69 Hoser A. 50 Itoh M. 19 Jorvinen G.D. 78 Hoskins B.F. 63 69 Iturbe J.L. 118 Jouini T. 10 Houle S. 127 Ivankina L.V. 63 Jubault M. 43 Hovey J.K. 69 Ivanov I.A. 131 Jung D. 24 Howlander M.B.H. 110 Iveges E.Z.110 Jung W.S. 110 Hoyer E. 74 75 Iverfeldt A. 74 Jyothi A. 112 Hsai C.M. 132 Iwamoto T. 38 Hu S. 65 Iwata C. 8 Kaba A. 117 Hua R.L. 121 Iwata R. 124 Kabalka G.W. 124 Huan G. 37 Izard M.E. 127 Kachab E.H. 63 Huang S.-P. 46 Izawa G. 128 Kadish K.M. 62 112 Huang T.C. 24 Kageyama A. 130 Hubert-Pfalzgraf L.G. 91 92 Jache A.W. 49 Kahlich S. 30 96 Jackson T.C. 30 Kai Y. 125 Huffman J.C. 111 Jacob A.T. 109 Kajewski J.J. 21 Huggins R.A. 28 Jacob K. 103 Kaldis E. 22 Hughbanks T. 82 Jacober S.P. 61 Kalinovskaya I.V. 85 Huhta D.W. 61 Jacobson A. 23 Kalinowski M.K. 18 Hui T.L.T. 12 Jakobs S. 53 Kallitsis J. 68 Huizenga J.R. 120 Jakubovic D.A. 66 Kalucki K. 59 Hummel H.-U. 29 James A.C.W.P. 21 35 Kalyanasundaram J. 62 Hunt R.D. 56 Janett A. 119 Kamata S.7 Hunt S.E. 64 Jankowski K.J. 17 78 Kaminek M. 122 Hunter C.A. 62 Janout V. 75 Kamiya Y. 84 Huo D.T.C. 15 17 Jansen S. 44 Kanagawa A, 117 Hursthouse M.B. 38 58 90 Jasionowska R. 67 Kanatzidis M.G. 17 42 46 Huskowska E. 91 95 98 Jastrzebski J.T.B.H. 71 Kane P.D. 121 Hussain B. 90 Hussey C.L. 6 Huszar I. 119 Jeffrey J. 63 Jegge J. 119 Jeitschko W. 81 Kanehori K. 22 Kanellos J. 126 Kanezaki E. 63 Hwang D.-R. 125 Jenkins R.W. jun. 133 Kang D. 35 HWU S.-J. 24 Jennings K.R. 109 Kang H. 69 Hyde T.I. 75 Jensen H. 132 Kanno T. 132 Jerez A. 47 Kanotzidis M.G. 25 Iahihara Y. 8 Jervis R.E. 132 Kapoor P. 51 Ibers J.A. 17 35 42 45 48 Jesih A. 54 Karasev V.E. 85 Ichihara J. 3 Ji D. 133 Karpiuk J. 88 Ichimasa M. 132 Jiang S. 122 Karthikeyan S. 96 Ichimasa Y.132 Jianhua W. 10 Kassyk A.L. 66 Ichiya Y. 124 Jie C. 74 Kataky R. 78 Ido T. 124 Jin J. 128 Katsuki T. 84 Ikari S. 35 Jin Y. 122 123 127 Katz J.J. 117 Ikemura T. 8 Jin Z. 17 Kau LA. 64 Ikewere P.O. 65 Jing X.Y. 90 Kaufmann K.D. 121 Il’in E.K. 91 Jivan S. 124 Kaushik N.K. 72 Imamoto T. 84 Johann R. 26 Kautek W. 12 141 Kavum V.Ya. 85 Kazikiewicz J.M. 127 Kazukov V.P. 88 Keenan S.R. 107 Keggan C.E. 66 Kegishi E. 69 Keim W. 83 Kelbaek H.,127 Keller C. 117 Keller H.J. 30 Keller O.L. 86 Kellett P.J. 47 Kelly P.F. 41 Kemp T.J. 109 Kendrick A. 27 Kennard C.H.L. 18 Kennedy J.D. 38 Kennedy M.A. 67 68 Kenny C. 84 Kentgens A.P.M. 13 Kepler J.A. 122 Kern J.-M.68 Kertscher U. 121 Khajamasthan S. 8 Khalifa S.M. 131 Khalili F.I. 99 Khalkin V.A. 120 Khan LA. 98 Khan R. 110 Khandelwal B. 31 Khandozhko V.N. 88 Khanna R.K. 71 Khizbullin F.F. 42 Khoo C.S. 65 Khopkar P.K. 112 Khosravi M.J. 88 Kibala P.A. 24 32 35 Kida S. 84 Kidani Y. 61 Kieboom A.P.G. 85 Kierkegaard P. 91 98 Kiers N.H. 103 104 Kiesewetter D.O. 125 Kihn-Botulinski M. 86 Kilbourn M.R. 118 125 Kilimov V.D. 91 Killa H.M. 71 Kim B. 67 Kim J.I. 131 Kim P. 14 Kim S.H. 75 Kimizuka N. 16 Kimura E. 39 62 75 Kimura T. 31 King M.P. 132 King R.B. 75 King W. 88 Kini A.M. 47 Kinrade S.D. 10 Kinumi Y. 63 Kioche T. 62 Kiseleva T.V. 80 Kishi T.45 Kishio K. 23 Kiso Y. 124 Kiss I. 128 Kiss T. 61 Kissane R.J. 109 Kita H. 15 Kitamura K. 7 Kitazawa K. 23 Kiwi J. 23 Kizilyalli M. 40 Kjekshus A. 48 Kjellstrom R. 118 Klaassen D.B.M. 40 Klapoetke Th.M. 51 Klapotke T. 41 Kleijn H. 63 Klein R.S. 122 Kleinert P. 127 Klemperer W.G. 24 Klenze R. 131 Kling P. 124 Klingert B. 63 Klinowski J. 7 Kmonickova E. 125 Knapp F.F. jun. 120 Kniep R. 7 Knoechel A. 124 Knoezinger E. 55 Knox S.J. 14 Koch S.A. 61 Koch W. 53 Kodama M. 75 Kodas T.T. 22 Kohn R.D. 108 Koenig H. 27 Koenig S.H. 86 Kohata S. 86 Kohler R. 75 Kohwa I.A. 102 Kojirna M. 125 Kolachkovski A. 118 Kolar Z.118 Kolis J.W. 37 Kornuro M. 132 Kondo Y. 124 Kondratenko R.M. 125 Kongpricha S. 49 Konishi J. 124 Koppe R. 29 Kortan R. 68 Kostikas A. 68 Kosuge K. 44,45 Koumanakos E. 68 Koura N. 4 Kourtakis K. 22 Koutsoukos P.G. 68 Kovach J.L. 132 Kovacheva S. 126 Kovacs J.A. 35 Kovacs Z. 119 Kovalik A. 133 Kovocheva D. 22 Kraft J. 28 32 Kramer A.V. 127 Kramer K.S. 80 82 Author Index Kramer U. 65 Kraml G. 71 Kranz G. 9 Krauss N. 51 Krebs B. 37 41 Kren R.M. 11 Krickemeyer E. 31 Krot N.N. 78 Krpejsova L. 125 Kruger C. 63 Kruger T. 37 Krulik R. 122 Kruz T. 120 Kuan K.T. 86 Kubo M.K. 134 Kuklik A, 133 Kulagina N.G. 80 Kuleshov S.P. 88 Kulugin N.M.80 Kumagoui N. 84 Kumar A. 11 Kurnar K. 77 Kumar R. 15 17 75 Kunchena B. 110 Kundu A.K. 6 7 Kung H.F. 127 Kunkely H.,71 74 Kuno H. 8 Kuppers H.J. 63 Kurbonbekov A. 89 Kurogi Y. 39 Kushita K. 119 Kustin K. 57 Kuvatov Yu.G. 125 Kuwabara Y. 124 Kwarteng-Acheampong W. 27 Kwik W.L. 66 Laakkonen L.J. 108 Laangstroem B. 123 124 Laborde E. 125 Lacroix P. 28 Lada E. 18 Ladriere J. 129 Lagrange J. 11 1 Lagrange P. 111 Lakshmi R. 133 Lalinda E. 64 Lamberts W. 106 Lambrecht R.M. 119 123 127 Lammertsma K. 3 12 Lamotte B. 30 Lamparter P. 7 Land E.J. 24 Landais P. 117 Lang R.W. 63 Langenbach-Kuttert B. 81 Langereis C. 24 Langford C.H.62 Lappert M.F. 63 78 94 104 Laptev D.M. 80 Larnelle P. 42 Larroque J. 77 Laruelle P. 14 Author Index Lasne M.-C. 123 Lathrop D. 42 Lad J.C. 131 Laurenczy G. 65 85 Lavery A.J. 26 Laville F. 9 Lawless G.A. 78 Lazurkina T.Y. 122 Le Bail A. 4 Leban I. 54 75 Le Bars D. 124 Lebedev N.A. 120 Lebedev N.I. 129 Lebedeva L.S. 120 LeBeuze A. 35 Lebioda L. 14 62 Lech L.M. 79 Lee B. 4 Lee G.S.H. 69 Lee H. 69 Lee P.R. 90 108 Lee S. 81 Lee T.J. 55 Lee T.Y. 132 Lee Y.W. 127 Leese T.A. 72 Leete E. 75 Legendziewicz J. 91 Le Greneur S. 121 Leinsten J.A. 57 Lejus A.M. 9 Lelieur J.P. 25 Leman J.T. 11 Lemoine P.P. 16 Lenstra A.T.H.65 Leon AS. 126 Leon E. 126 Leon P. 121 Leonard E. 84 Leong A.J. 68 Leong J. 63 Leovac V.M. 110 Lepoutre G. 25 Lerner M. 58 Leroi G.E. 62 Leschnitzer D.H. 65 Leszczynski J. 12 LCtoffC J.-M. 47 Leung L.K. 40 68 Levason W. 57 Lever S.Z. 127 Levet J.C. 48 Levstik M.A. 47 Ley S.V. 102 Li C. 80 Li H.-Y. 70 Li T. 127 Liang R. 19 Libertini E. 66 Liebman J.F. 53 Lierse C. 131 Liimatta E.W. 48 Likforman A. 16 Lincoln. J.. 51 95 98 Linde J. 127 Linden A. 28 Linder P.W. 65 Lindner L. 118 Lindoy A.J. 68 Lindoy L.F. 63 Lindsell W.E. 18 Lipscomb W.N. 61 Lis S. 95 Lis T. 5 Lisensky G.C. 40 68 Litoka Y. 42 Little I. 64 Little R.110 Liu B. 123 127 Liu J. 81 Liu R.S. 80 Liu Y.H. 112 Liu Z. 81 Lizano A.C. 32 Llobet A, 71 Lo J.M. 129 Lobana T.S. 72 74 Lobos S. 126 Loc’h C. 119 125 Lockemeyer J.R. 37 Loebel J. 90 108 Loffler J. 86 101 Lohmeyer M. 55 Lojou E. 6 Lok C.K.C. 84 Lokhande R.S. 130 Long G.J. 81 Lopez R. 67 Lopszewicz J.A. 83 Lorberth J. 71 Luchinat C. 61 Ludwig E. 126 Lueken H. 106 Luhrs E. 41 Lukaszewicz K. 14 Luke A.W. 26 Luna D. 11 Lutar K. 54 Luthra S.K. 124 125 Lutz T.G. 12 Luxen A. 124 LySka A. 103 Lynch V.M. 68 69 Ma H. 106 Ma I. 69 Ma T. 120 Maag R. 119 Mabrouk H.E. 15 17 64 Mabrouk P.A. 134 McAlees A.J. 72 McArthur M.J.62 McAughey J.J. 134 McCaleb C.S. 32 McCarron E.M. 24 McClure D.J. 72 McCollum G. 124 McConville D.H. 15 36 McCool B.J. 68 McCrindle R. 72 McCullough K.J. 18 MacDougall P.J. 53 MacDuff R.C. 17 McGarvey B.R. 15 McGauchan D.C. 72 McGeary M.J. 92 McGrady G.S. 29 Macias A. 19 72 MacKinnon P. 94 McKinnon W.R. 45 McLain S.J. 21 80 McLaren F. 62 Maclaurin C.L. 63 McLean R.S. 45 MacMahon T.J. 30 McMillan D.R. 74 McPartlin M. 68 McPherson G.L. 102 McRae D.D. 133 Maddalena D.J. 126 Madhusudan Raju R. 62 Maeda M. 125 Maggs A.A. 64 Magon L. 126 Mahjoub A.R. 50 Mahler C.H. 45 Mahler W. 29 Mahon M.F. 29 Maier-Borst W. 124 Maiti T.C. 131 Maitlis P.M.64 Maitrot M. 63 Maiya G.B. 62 Majumder S.M.M.H. 66 Mak T.C.W. 18 Makarov A.M. 129 Maksimovskaya R.I. 13 Malek A. 113 Malhotra G.L. 48 Malitesta C. 72 Mallouk T.E. 69 Malmborg P. 123 124 Mamantov G. 6 Mamo A. 67 88 Man S.F.P. 127 Manabue L. 65 Mancini A.C. 128 Manfredini T. 65 Mangani S. 62 99 Mani R.S. 119 126 133 Manivannan V. 48 72 Mannens G. 123 Mantese J.V. 7 Manziani M.C. 74 Manzini A. 127 Marangon G. 74 Marcalo J. 89 Marcandalli B. 131 March L.A. 65 74 Marchetti P.S. 68 Marchi A. 126 Margerum D.W. 51 Author Index Marinas J.M. 11 Mariscano F. 66 Markowitz M.A. 75 Marks A. 127 Marks L.D. 24 Marks T.J. 78 106 Marolleau I.86 Marques R.O. 119 Marquez R. 43 Marsden S.D. 65 Marsh P. 21 Marshall W.D. 128 Martell A.E. 12 66 Martin C. 19 Martin K.J. 65 Martincigh B.S. 66 Martinho-SimGes J.A. 71 113 Maruya K. 16 80 Maruyama K. 62 63 Maruyama Y. 119 Marziale D.P. 119 Masaki N.M. 128 Masana A. 70 Mascanzoni D. 133 Mason W.R. 72 Massa W. 71 Mastikhin V.M. 8 Mastryukova T.A. 129 Masuda K. 124 Masunaga T. 9 Mather S.J. j25 Mathey F. 106 Mathey Y. 35 Mathis C.A. 127 Mathur P. 31 48 Matsui H. 132 Matsumoto F. 79 89 Matsumura N. 89 Matsunaga T. 11 Matsuo A, 117 Matsushita H. 8 Matsushita T. 15 Matsuyama M. 132 Matthews B.W. 61 Mattson M.V. 125 Matusz M.32 Mauridis J.F. 78 Mausner L.F. 127 Mavunkal I.J. 48 May P.M. 66 Mayer H.J. 81 Mayo S.I. 62 Maziere B. 119 Mazumder S. 22 Mazzi U. 133 M’Boungou R. 75 Meah M.N. 62 Mease R.C. 127 Meerschant A. 35 Meetsma A. 105 Meguro K. 8 Mehrotra R.C. 17 Meijersink A, 87 Meinken. G.E. 127 Mekhail F.M. 132 Melichar F. 119 Melroy O.R. 7 Menabue L. 67 Menard H. 71 Meng M. 127 Meng Z. 122 123 127 Merbach A.E. 65 85 Mercier H. 42 Mertin W. 81 Merwin L.H. I1 Meske H. 29 Messina R. 6 Mestnik S.A.C. 119 Metabanzoulou J.P. 11 1 Metcalf D.H. 87 Metz W. 59 Mevs H. 81 Meyer G.J. 40 68 82 Meyer R.J. 130 Michel C. 19 23 Micheloni M. 62 67 Midollini S.64 Mihara T. 83 Mikros E. 63 Mikusik P. 133 Millar K. 78 Miller J.M. 63 Miller M.M. 23 Millican A.T. 17 78 Mills A. 83 Milone L. 74 Mimoto T. 124 Mimura H. 132 Min Y. 99 Minami E. 16 Minchenkova N.Kh. 83 Ming L.-J. 61 Mink J. 72 Miralles N. 70 Miralles P.D. 71 Miravitlles C. 71 Mirsaidov U. 89 Mishra S.P. 129 Misono M. 83 Mitchell A.J. 131 Mitta A.E.A. 126 Mittag E. 121 Miyake C. 109 Miyake H. 132 Miyake Y. 124 Miyauchi K. 22 Miyauchi M. 69 Mizuno M. 83 Mizutaru S. 7 Mni J. 126 Moberg C. 70 Mocala K. 23 Mock B.H. 127 Modro T.A. 65 Moefsma A. 104 Mohapatra P.K. 112 Mohri T. 16 Moinuddin Ahmed A.H. 9 Moise F.12 Molander G.A. 84 Molins E. 71 Moller K. 29 40 46 68 Molloy K.C. 29 Monakov Y.B. 83 Monberg C. 66 Mondry A. 85 Monnanni R. 61 Moore D.A. 14 Moore P. 62 63 Mootz D. 55 56 Moran E. 24 Morawski A.W. 59 Morelock M.M. 134 Moresco A. 133 Moret M. 65 Moreton A.D. 65 Morgan G.F.E. 126 Morgat J.L. 122 Mori A. 75 Mori K. 123 Morin C. 123 Morris D.E. 78 Moms S.A. 72 Morris V.,49 Morrison C. 123 Morrison J.A. 19 72 Morss L.R. 117 Morton R.C. 88 Mosier-Boss P.A. 4 Moskwa J. 118 Moss M.A.J. 96 97 98 Moulin V. 131 Moustier A. 122 Mridha M.U.A. 66 Muller A, 31 Mueller H. 129 Muller U. 29 Muller-Buschbaum H.K. 81 Muenze R. 126 Muhammed M.70 Muir K.W. 18 Mukundan S. 62 Mulder H. 40 Mulholland G.K. 118 Muller E.P. 74 Muller G. 74 Muller R.S. 16 Mullica D.F. 65 84 Munck E. 62 Munoz A. 43 Murai T. 68 Murakami M. 124 Muramatsu Y. 132 Murano Y. 128 Murata M. 132 Murinov Yu.I. 125 Muroi T. 86 Murphy E.P. 68 Murray G.M. 88 Murray K. 66 Murthy T.S. 119 Mushtaq A. 118 Author Index Mutsaers C.A.H.A. 24 Myasoedov N.F. 122 Nabiev Sh.Sh. 91 Nadal L.L. 70 Nadirashvili L.Sh. 128 Nagahama T. 8 Nagai M. 8 9 Nagamine K. 134 Nagase M. 66 Nagy J.C. 51 Naik R.M. 70 Nair C.G.R. 9 Nair H.K. 19 Nair V.C. 119 Nakagawa T. 110 Nakajima T. 58 Nakamura A. 36 61 Nakamura K.84 Nakamura M. 16 84 Nakamura T. 19 63 Nakanishi C. 130 Nalewajek D. 62 Nanbu H. 8 Nanjundaswanny K.S. 24 Natarojan K. 31 Nath B. 110 Naumann D. 51 53 70 Navrotsky A. 23 Nazzal A.I. 24 Nebeling B. 128 Neils T.D. 65 Neilson J.B. 72 Neufert R. 72 Newman P.D. 71 Newnham R.H. 94 Ney S.C. 72 Ngoviwatchai P. 71 Nicholls D. 66 Nichols D.E. 127 Nicolas C. 122 Nicolini M. 126 Niedrich H. 121 Nief F. 106 Nielsen S.L. 127 Nigam P.C. 70 Niisawa K. 123 Nishimaki K. 132 Nishioji H. 130 Nishisaka T. 63 Niu F. 120 Nobile C.F. 72 Noble M.E. 32 Noel H. 48 Nofz M. 9 Noguchi H. 132 Nolan S.P. 78 106 Noltemeyer M. 16 18 Nordin G. 80 Norris A.R.75 Nosov A.A. 119 Noth H. 27 Noto M.G. 127 128 Noujaim A.A. 127 Novgorodov A.F. 118 120 Nowell I.W. 65 74 Nozaki H. 35 Nozaki T. 123 Nriagu J.O. 67 Nuber B. 63 Nungesser N.A. 121 Nunn C.N. 69 Oakley R.T. 27 Oberdorfer F. 124 Ochiai H. 63 O’Donnell T.A. 50 Odriozola J.M. 65 Oehlke J. 121 Oesch F. 122 Oesterreicher H. 23 Oetvoes L. 124 Ofori-Okai G. 69 Ogawa K. 123 Ogden J.S. 57 Ogden M.I. 94 Ohana I. 59 Ohki Y. 79 Ohkubo M. 119 Ohman L.-O. 10 Ohmomo Y. 132 Ohtaki H. 69 71 Ohya-Nishigucti H. 109 Ohyoshi E. 86 Oiarbide M. 65 Okawa H. 84 Okura I. 63 Oldfield E. 80 Ollitrault-Fichet R. 47 Olmstead M.M. 75 Olofson J.M. 92 94 95 Olson B.L.23 O’Mahoney C.A. 26 102 Omenetto M. 111 O’Neal S.C. 37 Onishi T. 16 80 Onoda M. 35 Onopchenko A, 12 Ontiveros G.D. 72 Oohashi K. 123 128 Ooi B.-L. 32 Oppermann H. 71 O’Reilly E.J. 18 Orioli P. 62 99 Ormiston R.A. 121 Orpen A.G. 104 Orr R. 64 Ortiz-Avila C.Y. 65 Orvig C. 12 Osella D. 74 Ossola F. 113 Ossor H. 71 Osteryoung R.A. 4 Ostocoli G. 65 67 Osuka A. 62 63 Otsuka M. 124 Otto R. 125 Ouchi A. 71 79 89 Ozarowski A. 15 Ozawa T. 63 68 Ozeki T. 66 Ozutsumi K. 69 71 Pac C. 68 Padam G.K. 48 Padmanaban N. 9 Padmanabhan D. 133 Paine R.T. 96 Pajerski A.D. 63 Pajput A.M. 83 Palaniandava M. 65 Palazzi M. 40 Palmer H.E.133 Paloma C. 65 Pandey P.M. 126 Pandit M.Y. 11 Pang T. 108 Pantano C.G. 64 Paoletti P. 62 67 Papaefthymiou G.C. 30 31 Papaefthymiou V. 62 Pappalardo S. 67 Paranathaman M. 33 Pardi L. 81 85 95 Parent P. 122 Parise J.B. 24 Park K.D. 80 Park Y. 25 Parker D. 14 16 17 78 Parkin I.P. 25 26 41 Parkington M.J. 57 80 Parks E.J. 87 Parks M.E. 23 Parvez M. 63 Pascal J.L. 57 Pasler H. 132 Passmore J. 41 43 Pasterback R. 63 Paton A.D. 65 Patrizio S. 39 Patterson H.H. 6 Pattrick R.A.D. 30 Patwe S.J. 80 Pauwels E.K.J. 126 Pavlik I. 103 Pawlik M.J. 47 Payne G.F. 86 Pearlstein R.M. 134 Pebler A. 22 Pecksen G.N. 19 Pedersen K. 123 Pedley J.B.63 Pelevin L.A. 120 Pellacani G.C. 65 67 Pellinghelli M.A. 50 Peneloux A. 133 Peng C.T. 121 122 Peng H.B. 89 Penner-Hahn J.E. 74 Pennington M. 110 Pennington W.T. 4 12 Pentenrieder R. 58 Author Index Perdicakis C. 122 Perec M. 69 Perichet G. 75 Pirichon J. 6 84 Peringer P. 74 Perlmutter M. 124 Pernot P. 59 Persson A. 123 Persson I. 74 Peshev P. 22 Pesterfield L.L. 88 Peters J.A. 85 Peters K. 103 Petillon F.Y. 33 Petit-Ramel M. 75 Petri H. 125 Petrov K. 22 Peyroutou C. 42 Peytavin S. 42 F'feffer M. 39 71 Pfennig B.W. 88 Pham P. 122 Philippot E. 11 Phillips C.R. 132 Phillips M.W. 10 Phipps A. 17 Picha J. 122 Pichat L.122 123 Pichova D. 122 Pickardt J. 108 Pico C. 47 Pietraszkiewicz M. 88 Pike G.A. 62 Pike V.W. 123 124 125 Pilloud F. 86 Pinkerton A.A. 10 Pinto-Alphandary H. 122 Pirat J.-L. 125 Pires A. 89 Pires de Matos A. 78 Piro O.E. 61 Piscator M. 67 Pitteri B. 74 Pitts J.J. 49 Pla-Dalmau A, 71 Plambeck-Fischer P. 47 Plankey B.J. 6 Plasencia M.M. 72 Platt A.W.G. 110 Platt K.L. 122 Plechaty M.M. 23 Plet F. 3 Pluzinski T. 5 Pock W.F. 21 Poeppelmeier K.R. 24 Pohl S. 63 67 Pojer P.M. 125 126 Polak P. 118 Poll w. 55 Polo A. 100 101 102 Poncelet O. 91 92 96 Pons J. 65 Poon S.J. 21 80 Pope J. 126 Poppalardo S. 88 Porchia M. 113 Porte L. 63 Porto R.85 Post M. 132 Potier J. 57 Poupeye E. 123 Pouyet B. 75 Povey D.C. 72 74 Powell J.E. 112 Pozzi A, 65 Pradeep T. 28 Pramanik P. 46 Prassides K. 80 Premuzic E.T. 131 Prestwich G.D. 122 Pritchard J.N. 134 Prokop J. 119 Prosser-McCartha C.M. 62 Provost J. 19 23 Pruliner J.D. 80 Ptaziak A.S. 95 Puddephatt R.J. 39 Purkayastha R.N.D. 109 Pyykko P. 108 Qaim S.M. 118 119 Qi Z. 130 Qitao L. 67 Que L. 62 Quershi M.A. 119 Quintana P. 13 Rabenstein D.L. 74 Rabiller G. 127 Rabu P. 35 Rack E.P. 130 Radchenko V.M. 120 Radecko-Paryzek W. 100 Radom L. 53 Ragosta J.M. 74 Rahman A.A. 66 Rai A.K. 17 63 Rajagopal H. 24 Rajumon M.K. 80 Ram S.123 Ramamoorthy N. 119 Ramdas V. 72 Ramirez F.P. 127 Ramirez F.de M. 118 Ramshesh V. 130 Randrianohavy J.V. 12 Ranganatha D.K. 133 Rankin D.W.H. 27 29 Rao B.S.M. 129 Rao C.N.R. 24 28 Rao G.N. 112 Rao G.N.R. 80 Rao G.R. 80 Rao K.V.C. 9 Rao T.R. 98 Rao U.K. 80 Rao V.R.S. 125 Rao V.V.. 8 Rashes I. 23 48 Rastovac M. 126 Ratner M.T. 128 Ratti C. 35 Rau M.S. 64 Rauchfuss T.B. 37 Raveau B. 19 23 Ravert H.T. 123 Read P.A. 109 Reader C.J. 63 Reboso R. 66 Recknagel A. 107 Reed A.E. 3 Reed C.A. 62 Reedijk J. 65 67 71 Refosco F. 133 Regen S.L. 75 Reger D.L. 14 Rehder D. 79 Reich E. 119 133 Reichert T. 133 Reichstein E. 88 Reid G.26 75 Reier F.W. 108 Reilly R. 127 Reissel A, 118 Reppart W.J. 18 Retoux R. 23 Rettig S.J. 12 Rey P. 81 85 95 Rheingold A.L. 37 88 92 Rhind S.K. 17 Rhodes C.J. 72 Rhodes L.F. 113 Ribbe P.H. 10 Ribes M. 42 Rice D.A. 65 Rice D.E. 120 Rice K.C. 125 Richard P. 35 Richardson F.S. 87 Richardson J.F. 32 Richardson M.F. 63 Richey H.G. 63 Richter R. 75 Riehl J.P. 87 Rieksts G.A. 133 Righetto L. 131 Rihs G. 63 Riou A. 20 Ritchey J.M. 113 Rius G. 30 Rivero B.E. 61 Rivet J. 47 Rivier H.O. 83 Rizkalla E.N. 112 Rizzarelli E. 65 67 Rizzo L. 109 Robbins M. 22 Robertson B.E. 65 Robertson H.E. 27 29 Robini P. 70 Robinson G.H. 4 12 Robl C.66 Author Index Robouch P. 131 Robson R. 63 Rocco J.C. 128 Rode B.M. 67 Rodehuser L. 70 Rodriguez A. 66 Rodriguez-Arguelles M.C. 19 Roe D.C. 126 Roe S.M. 62 63 Roemer J. 121 Roesky H.W. 16 18 107 Rogers R.D. 105 111 Roland P. 123 Rollins A.N. 11 1 Romero M.A. 67 Ronda C.R. 9 40 Rondaccio L. 80 Rone V.H. 83 Roques B.P. 121 Rosen S.T. 127 Rosenberg E. 74 Rosseinsky M.J. 80 Rossetto G. 113 Rotaiczak R.D. 44 Roth N.P. 62 Roth S. 113 114 Rousseau B. 121 122 Rousseau D. 113 Rousseau J.J. 12 Rouxel J. 35 Rowley S.P. 75 Royan B.W. 28 29 Rudolf P.R. 65 Rudolph B. 15 Riiter I. 81 Rugmini V. 48 Rulmont A. 48 Rundberg R.S. 131 Rupp L.W.21 Ruren X. 10 Rusiecki S. 22 Russell D.R. 110 Russell G.A. 71 Russo U. 90 Ruth T.J. 123 Ryabinin M.A. 120 Ryan R.R.,78,96 113 115 Ryan T.A. 57 80 Ryley G. 123 Rysavy M. 133 Rzepa H.S. 26 Saad Z. 62 Saak E. 63 Saak W. 67 Sabatini A. 50 Sabbatini L. 72 Sabirov Z.M. 83 Sabourin E.T. 12 Sabu K.R. 9 Sacco A. 72 Saeki M. 35 128 Sahleid T. 82 Saillard J.-Y. 33 St. Clair M.A. 79 Saito T. 33 Saji H. 124 Sajjad M. 119 127 Sakaguchi M. 63 Sakai Y. 130 134 Sakamoto Y. 8 Sakata Y. 83 Sakkopoulos S. 68 Saladini M. 67 Salas J.M. 67 Salazar K.V. 113 Saleh R.J. 62 Sales K.D. 90 Salifoglou A. 68 SallC M. 43 Salvador P. 23 Samad S.A.3 Sambre J. 124 Sameh A.A. 79 108 Sameh A.H.A. 119 Sammartano S. 67 Sammells A.F. 17 Sanami M. 42 Sanchez A. 19 67 72 Sanders J.C.P. 53 Sanders J.K.M. 62 64 Sanders J.R. 6 Sandhu M.K. 72 74 Sandiumenge F. 10 Sandman D.J. 44 Sandor R.A. 24 Sandor R.B.W. 32 35 Sang Y.P. 99 Sangokoya S.A. 4 12 Sanni S.B. 65 Sano H. 129 Sano M. 68 Sansare S.D. 11 Santos I. 78 Sanz G. 125 Sappenfield E.L. 65 Sarkar B.R. 119 Sarma D.D. 80 Same G. 6 Sartain W.J. 91 Sasaki K. 61 Sasaki Y. 35 Sastre A.M. 70 71 Sato H. 23 Sato T. 47 78 Satoh K. 70 Sattelberger A.P. 11 1 112 113 115 Saulys D.A. 72 Saussino L. 83 Sauvage J.-P. 62 68 Savas M.M.72 Saver N.M. 113 Sawada G. 8 Sawada K. 70 Sawyer D.J. 112 Sawyer D.T. 25 Sazou D. 62 Schaber P.M. 62 Schaedel M. 120 Schafer A. 63 Schaffrath U. 81 Scharbert B. 101 Scharfi P. 59 Schatte G. 55 Schausten B. 120 Schaverien C.J. 104 Scheffel U. 123 Scheidt W.R. 62 Scheller D. 126 Schindler A.I. 23 Schladerbeck N.H. 31 Schleyer P.von R. 3 Schlyer D.J. 118 Schmalle H. 61 Schmidt K.J. 26 Schmidt R. 24 Schmidt-Klemens A. 74 Schmiedova D. 127 Schmite J. 106 Schmitz K. 31 Schnockel H. 29 Schoeps K.-O. 123 Scholten B. 119 Scholz M. 16 18 Schornstein H. 75 Schreiner S. 35 Schrems O. 55 Schrobilgen G.J. 53 Schroder A.M. 128 Schroder M. 26 75 Schroter C.9 Schulz F. 59 Schulz M. 82 Schumann H. 90 107 108 Schwarz W. 103 Schwarzbach R. 118 Schweitzer D. 30 Schweitzer G.K. 88 Schwenner E. 123 Schwing-Weill M.J. 86 Schwochau K. 126 Scilla G.J. 23 Scott B. 126 Scozzafava A, 61 Scudder M.L. 40 66 69 Seaborg G.T. 117 Sebald A. 11 Sebban M. 63 Seddon K.R. 57 80 Sedvall G. 123 Seleznev A.G. 120 Self M.F. 4 Selvaraj S. 127 Sen A. 92 Sensui Y. 129 Seppelt K. 50 Sequeira A, 24 Serezhkin V.N. 109 Serezhkina L.B. 109 Sessler J.L. 68 86 Setiabudi F. 122 Seudeal N. 15 Seyam A.F. 99 Shachter A.M. 63 Shafer M.W. 23 Shakir K. 132 Shalimoff G. 108 Shantha Nandana W.A. 43 Sharma D.K.62 Sharma H. 118 Sharma H.L. 119 Sharp C. 32 Sharpe N.W. 99 Shashukov E.A. 131 Shatkov V.M. 131 Shaver C.K. 99 Shaviv R. 48 Sheldon K. 127 Sheldrick W.S. 74 75 Shelnutt J.A. 62 Sherry A.D. 86 Shevchenko V.P. 122 Shi Y. 127 Shibagaki M. 8 Shibahara H. 24 Shibahara T. 32 Shibuya A. 47 Shieh M. 65 Shimada M. 47 Shimoda M. 42 Shimoni M. 121 Shinde S.N. 119 Shinmyozu T. 84 Shionoya M. 39 Shiragami T. 68 Shirahashi K. 128 Shono T. 15 Shore S.G. 89 Short R.L. 38 Shorygin P.P. 72 Shouhua F. 10 Shu H.W. 47 Shuin Y. 84 Shulgin A.T. 127 Shum D.P. 81 Shushakov V.D. 120 Shuslov L.D. 91 Shuvalov B.N. 120 Siddique R.M. 19 Sidiqui M.R.H.3 Siegrist T. 68 Sieler J. 74 75 103 Silar J. 133 Sill C.W. 132 Simard M. 16 Simmons C.A. 28 Simon A, 103 Simon-Trompler E. 124 Simopoulos A. 68 Simoyi R.H. 57 Simpson D.J. 61 Sing S.K. 17 Singh A.K. 122 Singh B. 98 Singh G. 98 Singh J. 129 Singh P.K. 98 Singh Y. 17 Sinitsyn V.I. 109 Sinn E. 17 64 Sinnema A. 85 Sinning H. 29 Sironi A. 65 Skelton B.W. 94 Skowron A. 29 Skyllas-Kazacos M. 3 Skytte Jensen B. 132 Slawin A.M.Z. 25 26 41 Slegers G. 123 Sleight A.W. 21 24 80 Slovak Ya. 120 Slowey P.D. 121 Slusarenko V. 23 Smailes D.L. 102 Smeets W.J.J. 63 104 Smets B.M.J. 9 Smith A.G. 119 Smith A.M. 119 Smith D.E. 18 Smith F.E.66 Smith G. 18 Smith G.W. 72 74 Smith J.D. 70 72 Smith J.M.A. 16 Smith K.M. 61 Smith M.G. 23 Smith M.R. 131 Smith P.H. 78 Smith R.G. 104 Smith S.V. 63 Smith-Jones P. 118 Sneddon D.W. 72 Snowdon G.M. 126 Snyder S.W. 87 Sobotoa P. 5 Sodhi G.S. 72 Soedervall M. 127 Sola M. 45 67 Soldi T. 126 Solin O. 118 Solomon E.I. 64 Soman P.D. 133 Sondergaard A.P.L. 6 Song H. 62 Sontasiero D. 79 Sorby P. 127 Sordo J. 19 72 Souers P.C. 117 121 South T.L. 67 Sovago I. 61 Spalding T.R. 38 Spek A.L. 63 104 Spencer R.P. 120 Spicer L.D. 123 Spicer M.D. 57 Spies H. 126 Spies S.M. 127 Spiller M. 86 Author Index Spiro T.G. 31 Spitz H.B. 133 Sponsler M.B.53 Sprague J.B. 67 Sprinkle C.R. 75 Squattrito P.J. 65 Srdanou G. 30 Sreekanth K.S. 28 Sriovastava S.K. 45 Srivastava S.C. 127 Stack T.D.P. 30 Stadler S. 131 Staikov G. 15 Stalke D. 107 Stalla B. 27 Stec B. 62 Stecher H.A. 92 Steeb S. 7 Steigerwald M.L. 64 68 75 Steinmann G. 81 Stella R. 126 Steokewski Z. 127 Stepushkina V.V. 120 Steren C.A. 61 Stem D. 106 Stiefel E.I. 33 Stillman M.J. 74 Stober R. 9 Stoecklin G. 118 119 121 124 Stoeppler M. 67 Stone-Elander S. 123 Storch W. 27 Storowieyeski K.B. 63 Storozhenko P.A. 63 Stoutland P.O. 53 Strasdeit H. 67 Straub D.K. 62 Straughan B.P. 64 Strauss S.H. 47 Streib W.E. 92 111 Strelow F.W.E.118 Streltsova N.R. 63 Strijckmans K. 124 Strittmatter R.J. 113 Strunck A. 75 Strunecka A. 125 Strydom C.A. 81 Strydom H.J. 81 Strzelbicki J. 66 Stucky G.D. 40 46 68 Stuczynski S.M. 64 68 Stump N.A. 88 Stump R.K. 117 Stupin V.A. 120 Styring P. 64 Suarez M.I. 19 72 Subba Rao G.V. 33 Sugawara T. 61 Sugii N. 22 Suglobov D.M. 78 Sukhovskii A.A. 42 Sullivan A.C. 70 Sullivan J.C. 112 Sum E. 3 Author Index 149 Summers M.F. 66 67 Sunderlin L.S. 79 Surampudi S. 5 Susiki T. 70 Susla M. 84 Suslick K.S. 64 Suzuki K. 23 117 Suzuki T. 30 Suzuki Y. 79 89 Svensson G. 70 Svoboda K. 119 Swaddle T.W. 10 Swain A.L. 67 Sykes A.G.32 Szabo J.P. 68 Szammer J. 124 Szpak S. 4 Szpoganicz B. 12 66 Szweryn B. 120 Tabard A. 35 Tadzer I. 126 Takahashi K. 8 124 Takahashi Y. 70 Takai T. 63 Takami N. 4 Takamuku T. 71 Takayama-Muromachi E. 23 Takeda Y. 18 Takeshita H. 75 Takesue T. 8 Takeuchi A. 99 Takeuchi T. 66 89 132 Takeuchi Y. 42 Takiyama N. 84 Talarmin J. 33 Tamai N. 63 Tamaru K. 38 Tamaru Y. 63 Tan C.S. 132 Tanada S. 123 Tanaka K. 31 Tanaka M. 15 Tanaka T. 31 Tang G.Z. 122 Taniguchi M. 71 Tannor D.J. 24 Taqui Khan B. 62 Taqui Khan M.M. 3 Tarafder M.T.H. 110 Tarkanyi F. 119 Tarte P. 48 Tashtoush H.I. 71 Tasker P.A. 68 Tatsumi K. 36 108 Tattershall B.W.28 42 Taube R. 103 Tauler R. 66 Tavakkoli K. 70 72 Tay A.W.N. 66 Taylor G.F. 122 Taylor L.F. 47 62 Tebbe K.-F. 19 51 Tebby J.C. 110 Tedenac J.C. 47 Tedroff J. 123 Teixeira C. 71 113 Teixidor F. 65 71 Teng J. 120 Teuben J.H. 103 104 105 Tewson T.J. 118 Texier F. 43 Thampi K.R. 23 Thanyasini T. 64 Thayer A.M. 68 Theobald A.E. 126 Thery J. 9 Thieffry C. 35 Thiele K.-H. 63 103 Thomas-David G. 75 Thomason H.P. 131 Thompson D.M. 65 Thompson M.E. 88 Thompson R.C. 50 Thompson R.G. 47 Thorell J.-O. 123 Thornback J.R.,126 Thrasher J.S. 72 Tiekink E.R.T. 69 72 Tien V. 37 Tietz F. 23 Tilley R.J.D. 29 Timofeev S.A. 130 Tippin D.B. 65 Tisato F.133 Titov M.I. 121 Tittes K. 103 Tizot A. 121 Tocher D.A. 72 Toerien F.von S. 118 Tokmacheva N.S. 91 Tolley D.M. 125 Tolman V. 122 Tolstikov G.A. 88 125 Tomas A. 16 Tominaga T. 130 134 Tomiyasu H. 110 Tomoda S. 42 Tomura K. 129 Toriumi K. 62 Torniainen P. 127 Tornieport-Oetting I. 51 Torrance J.B. 24 Torres R.A. 86 Torrington R.G. 65 Torstenfelt B. 131 Toth I. 12 Touhara H.,58 Trautmein A.X. 31 Trisak S.T. 67 Trnka J. 71 Trogu E.F. 50 Tronc E. 9 Trout T.K. 87 Trunov V.K. 109 Tsai P.P. 37 Tsang H.-T. 74 Tseng C.L. 129 Tsetskhladze T.V. 128 Tsibakhashvili N.Ya. 128 Tsiganok L.P. 13 Tsirlin V.A. 120 Tsuchiya S. 83 Tsugawa R.T.117 Tsutsui T. 132 Tsutsumi D. 124 Tsvetkov F. 75 Tuck D.G. 13 15 17 64 Tulip T.H. 126 Tumllas X.M. 48 Turton D.R. 123 TUNey K. 65 Tyrra W. 51 53 70 Udagawa Y. 110 Ueda Y. 44,45 Ueki O. 8 Ueyama N. 61 Uezumi S. 31 Uhlemann E. 126 Ulibarri T.A. 81 106 Ulin J. 123 Underhill A.E. 30 38 Unoura K. 33 Uosaki K. 15 Urland W. 6 23 47 82 83 Usami S. 132 Ushakov V.P. 91 Usuanmaz A. 40 Usuda S. 120 Utko J. 5 Winkler J.R. 61 Winpenny R.E.P. 72 90 98 Winter G. 69 Winterberger M. 37 Withnall R.,49 Wolcyrr M. 14 Wold A. 28 39 Wolf A.P. 118 Wolmershauser G. 26 Wolsey W.L. 86 Wong C.-M. 43 Wong M.W. 53 Wood P.T. 28 Woods M. 112 Woollins J.D.25 26 27 28,41 Wraggs M.S. 64 Wright T.C. 69 Wu D. 122 Wu P. 28 39 Wu P.T. 80 Wu S. 87 Wu Y. 127 Wu Z. 106 122 Wudl F. 30 Wyand A, 118 Wynn J.D. 15 17 Xie J. 122 Xie L. 9 Yaghi O.M. 24 Yamaashi Y. 119 Yamada S. 99 Yamagata T. 33 Yamagishi A. 38 Yamagishi I. 132 Yamamoto I. 117 Yamamoto T. 23 Yamasaki H. 61 Yamashita S. 61 Yamashoji Y. 15 Yamazaki I. 63 Yamazaki S. 124 Yamochi H. 30 Yan M.F. 15 17 Yanagida S. 68 Yanai K. 123 Yang D.J. 125 Yang L. 106 122 Yang S. 80 Yassine T. 129 130 Yasuoka N. 61 Yazdi S.N. 72 Ye Z. 106 Yee K.A. 24 Yeh S.J. 129 Yellowlees D. 63 Yi C. 128 Yi L. 67 Yi M. 122 Yip W.H.18 Yokoyama A. 117 124 Yongxiang M. 99 Yoshida Z. 63 Yoshihara K. 128 Yoshikawa A. 33 Yoshinobu M. 83 Youfeng H. 119 Young A.B. 125 Young N.A. 57 Yousif Y.Z. 109 Yu J.C. 40 68 Yukawa Y. 66 Yun M. 99 Yunlu K. 94 95 Yus M. 71 Zakeeruddin S.M. 62 Zalkin A. 106 Zamani K. 122 Zambonin P. 72 Zanati H. 32 Zanchini C. 64 Zanella P. 113 Zangrando E. 80 Zanotti L. 15 Zarli B. 90 Zatta P. 11 Zawodzinski T.A. jun. 4 Zaworotko M.J. 4 Zeelie B. 109 Zekany L. 12 Zelinski A. 118 Zemva B. 54 Zerbinati O. 67 Zerner B. 62 Author Index Zhang C. 122 Zhang L. 122 134 Zhang P. 130 Zhang S. 128 Zhang X. 121 122 Zhang Y. 82 Zhang Z. 12 Zhao B.81 Zhao H. 128 Zhe W. 124 Zheng D. 122 Zheng S. 127 Zhennan Z. 104 Zhong M.J. 90 Zhongqian M. 99 Zhongwen Y. 104 Zhongzhik W. 104 Zhou Z. 106 Zhu L. 127 Zhu W. 23 Zhu Z. 128 Zhuangyu Z. 126 Ziegler T. 26 Ziller J.W. 11 92 94 95 103 Zimmer A.M. 127 Zmbova B. 126 Zu Z. 81 Zubieta J. 69 Zulfequar M. 11 Zvara I. 120 Zweit J. 118 119 Zwernemann O. 124

ISSN:0260-1818    

DOI:10.1039/IC9898600135

出版商:RSC    

年代:1989

数据来源: RSC