ISSN:0260-1818    

DOI:10.1039/IC99390FX001

出版商:RSC    

年代:1993

数据来源: RSC

ISSN:0260-1818    

DOI:10.1039/IC99390BX003

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

3 Al Ga In and TI By J.P. MAHER School of Chemistry University of Bristol Bristol BS8 1 TS UK This review has been constructed In the same fashion as last year namely by means of a computer search of the literature for papers related to the chemistry of the title elements. In order to maintain continuity with last years search a number of references which appeared at the end of 1992 but which were not covered in 1992 are included. The number of references detected is about 300 greater than in 1992 that is 3900 in all and the proportion of papers abstracted element by element remains as 70% aluminium 15% gallium 10% indium and 5% thallium. This is thus as ever a huge subject so that only some of the highlights are described -this year I have put more emphasis on the organometallic compounds of group 13 have included a section on bioinorganic chemistry and since the areas of interest seem different from last year other sections have been rearranged.1 Organometallic Highlights Volume 449 of the Journal of Organometallic Chemistry was devoted to the use of organometals in materials science and a considerable proportion of the papers concern various aspects of Group 13 organometal chemistry. The dominant feature of the alanes R,Al has always been their ability to form dimeric bridged compounds; an interesting series of organoaluminium imine com- plexes [RCH=NAlR,] have been prepared by the reaction of dialkylaluminium with nitriles. Thus the reaction of I-IAl(Bu') with the nitriles RCN (R = Me But CH,=CHCH, CH,=C(CH,) Ph (2-Me)Ph and (2,6-Me)Ph) leads to compounds which are dimeric in solution and in the solid state.The X-ray crystal structure of [(2,6-Me)PhCH=NA1(But),] was determined .' 1,3-diaryltriazenido aluminium compounds are monomeric. Thus reaction of HAl(Bu') with 1,3-diphenyltriazene (Ph)NNN(H)(Ph) (RN) together with ligand exchange reactions led to Al(Bu'),(R,) Al(Bu')(R,), and A1(RN),. X-Ray crystal structures for Al(Bu'),(R,) and for a number of other related compounds were described. The 'H 13C l7O 27Al NMR- infrared- and mass-spectrometry of [Me,Al(OR)] (R = Me Et Pr" Pr' Bun Bu' Bus But n-C5Hll CH,CH,Pr' CH,Bu' n-C6H13 n-C,H,, n-C,,H,, and n-C,,H,5) have been examined. The compounds with branched alkyl chains are all dimeric i.e. the exception being when J.A.Jensen 1.Organornet. Chem. 1993. 456 161. J.T. Leman J. Braddock-Wilking A.J. Coolong and A. R. Barron Inorg. Chem. 1993 32 4324. 25 J. P. Maher R = CH,CH,Pr'. In solution influenced by steric interactions and by ring strain the n-alkyl derivatives and CH,CH,Pr' all exist as a mixture of dimers and trimers. Equilibrium constants for the dimer-trimer equilibria were studied and ther-modynamic data obtained. The novel Al-As dimers [Bu~AlAs(SiMe,),] and [Me,AlAs(SiMe,),] were formed by reaction between LiAs(SiMe,) and R,AlCl (R = Bu' Me). The X-ray crystal structure of the iso-butyl compounds was determined. Interest in these compounds stems from their possible involvement as precursors in the formation of aluminium-arsenic semicond~ctors.~ Related to these compounds and reported by the same research groups are the four dimers [R(Me,SiCH,)InE(SiMe,),] (R = Ph E = As; R = Me E = As; R = Me E = P; R = C1 E = P).5 The reaction of BuiAl with phosphine or arsine forms cyclic trimeric compounds [Bu\Al(p-EH,)] (E = P As); related compounds with gallium in place of aluminium and also with E = N 0 were described.6 Subs tit uted aluminacyclopent- 3-enes [meso-(RC (Me ,Si)HC),A1(C1)NMe ,CH ,] were formed in a stereo-specific reaction between [{ Li(TMEDA)},{ Me,SiCHCR),}] (R = H Me) and AlCl in diethyl ether.The structure assignments were based on NMR and on an X-ray crystal structure determination.' The methylene bridged compound [(Me,Si),CH],AlCH,Al[CH(SiMe,),] reacts with neopentyl lithium in the presence of TMEDA to form ([(Me,Si),CH],- AlCH,Al[CH(SiMe,),],CH2CMe3} {Li(TMEDA),} there is no additional bridging and the new substituent occupies a terminal position.' The addition of Bu'PH or Bu'AsH to BuiAl or BuiGa followed by heating or photolysis of the complexes which form produced phosphido- and arsenido-bridge compounds of aluminium and gallium of composition [BuiM(p-E(Bu')H] (M = Al Ga; E = P As; y1 = 2,3) and which formed dimers or trimers.' A six-membered (Gap) ring with a chair conformation was observed for the compound [(Me,CCH,)ClGaPPh,] with the bulky neopentyl groups occupying E A A positions.The related compounds [(Me,CCH,)BrGaPPh,] and [(Me,CCH,)CIInPPh,] ,were also prepared. These are all compounds in which the metal carries three different substituents -a metal-halogen a metalkarbon and a metal-pnictogen bond.The X-ray molecular structure determination of [Me,GaP(Me)(Ph)] shows that this also contains a (Gap) ring with a chair conformation with the phenyl groups in axial positions.' ' A tetramer of composition [InC(SiMe,),] with an In core has been characterized. This unusual material formally an In' compound was prepared by reaction of InCl with [LiC(SiMe,)],,,.THF in diethyl ether. The average In-In bond distance in the core is 3.09(2)A.12 J. H. Rogers A. W. Apblett W. M. Cleaver A. N. Tyler and A. R. Barr0n.J. Chem.Soc.. Dalton Trans. 1992 3179. R. L. Wells A T. McPhail and T. M. Speer Eur. J. Solid State Inorg. Chem. 1992 29 63. ' R.L. Wells A. T. McPhail L. J. Jones 111 and M. F. Self J. Organornet. Chem. 1993 449 85. 'D.A. Atwood A. H. Cowley P. R. Harris R. A. Jones S. U. Koschmieder C. M. Nunn J. L. Atwood and S.G. Bott Organornetallics 1993 12 24. ' M.G. Gardiner and C. L. Raston Organornetallics 1993 12 81. W. Uhl M. Koch and A. Vester Z. Anorg. Allg. Chem. 1993 619 359. 'D. A. Atwood A. H. Cowley P. R. Harris R. A. Jones S. U. Koschmieder and C. M. Nunn,J. Organomet. Chem. 1993 449 61. lo O.T. Beachley J. D. Maloney and R. D. Rogers J. Organornet. Chem. 1993 449 69. 'I O.T. Beachley T. L. Royster Jr. J. R. Arhar and A. L. Rheingold Organometallics 1993 12 1976. l2 R.D. Schluter A. H. Cowley D.A. Atwood R.A. Jones and J. L. Atwood. J. Coord. Chem. 1993,30,25. A! Ga In and TI 27 The first indium-phosphorus heterocubane compound formed by reaction of Li,[PSiPh,] with (PrInIz)-Pri namely ([PrIn(p3-PSiPh3)],-Pr' has been character- ized by means of an X-ray crystal structure deterrninati~n.'~ Both Ga,N and In,N cubes are also observed in the new perfluorophenyl compounds (C,F,NGaMe) and (C,F,NInMe) which are formed by the reaction between Me,Ga or Me,In and C,F,NH in toluene followed by heating of the solid intermediate.'* Novel cage compounds { (Et20),Li){ Bu'Ga}{ PBu'},{GaBu\} and { Bu',Ga}(Bu'Ga){ PBu') {GaBu;) have been formed by the reaction of Li,PBu' with one or two equivalents of Bu\GaCl in diethyl ether.They were characterized by means of variable temperature 'H and ,'P NMR as well as by X-ray crystallographic measurements.Each have distorted trigonal bipyramidal cores with LiGa,P and Ga,P units respectively and each compound contains both three- and four-coordinate gallium centres.' Whilst dimers trimers and polymers are common molecular forms for many group 13 organometallic species it is also possible to force the formation of monomers by using bulky ligands. The compounds Bu'GaP(R)(SiPh,) where R is various bulky phenyl groups are examples.'6 A rotational barrier of 53 kJ mol-for the Ga-P bond was found from variable temperature 'H NMR measurements and was attributed to weak Ga-P n-bonding. Bu',Ga reacts with triphenylmethanol to form the monomer Bu\Ga(OCPh,) in which the gallium is three-coordinate. A rather short Ga to Ph intramolecular contact may possibly be due to interaction between the phenyl ring n-electrons and the vacant p orbital on the ga1li~m.l~ Me3Al reacts with two equivalents of the phenolic compound (O=C)(OMe)C,H,- o-OH to form the first X-ray crystallographically characterized mononuclear five- coordinate aluminium chelate complex MeA1[O=C(OMe)C,H,-o-O]z.l 'The first example of a five-coordinate tris-organogallium complex of composition (o-(CH,NMe,)C,H,),Ga has been reported." The compound achieves five-coordina- tion by axial coordination to two of the NMe groups whilst the remaining NMe group is pendent." Primary amines usually react with alanes through an elimination reaction however Ph,Al forms a monomeric (1 1) complex with Bu'NH,.This complex was character- ized by an X-ray crystal structure determination.20 Low temperature hydrolysis of Bu' A1 in pentane forms the trimer [Bu\AI(p-OH)] 3 thermolysis of this material leads to hexameric and nonameric aluminoxanes.Tetramers and octamers were also reported.,l Group 13organometallics are found in some interesting situations and with unusual coordinations. One of the products of PrlInCl with KF and 15-crown-5 acetonitrile is the crown ether salt [K( 15-crown-5),][Pr~InC12 TetrakisCbis(trimethy1-silyl)methyl]dialane a compound with an AI-A1 bond reacts with carbon disulfide inserting the CS unit into the AI-A1 bond; one of the products is a dithiocar- boxylate-type of derivative with the central carbon of the carbon disulfide bound to l3 D.A. Atwood A.H. Cowley R.A. Jones and M.A. Mardones J. Organomet. Chem. 1993 449 Cl. l4 T. Belgart H. W. Roesky M. Noltemeyer and H.-G. Schmidt Angew. Chem. Znt. Ed. Engl. 1993,32,1056. l5 M.A. Petrie and P. P. Power Organomt'tallics 1993 12 1592. l6 M.A. Petrie and P. P. Power J. Chem. SOC.,Dalton Trans. 1993 1737. W. M. Cleaver and A. R. Barron Organometallics 1993 12 1001. J. Lewinski J. Zachara B. Mank and S. Pasynkiewicz J. Organomet. Chem. 1993 454. 5. D. A.K. Coggin P. E. Fanwick and M. A. Green J. Chem. Soc. Chem. Commun. 1993 1127. 2o M. D. B. Dillingham S.J. Schauer W. T. Pennington and G.H. Robinson J. Coord. Chem. 1993,30 19. M.R. Mason J.M. Smith S.G. Bott and A.R. Barron J. Am. Chem. SOC. 1993 115 4971. 22 B. Neumuller F. Gahlmann M. Schafer and S. Magull J. Organomet. Chem.1992 440 263. 28 J. P. Maher one aluminium and the two sulfurs chelated to the second al~minium.’~ Six-membered heterocycle compounds of the type Me,GaCH,PMe,BH,CH,N Me and Me,GaCH,NMe,BH,CH,NMe, with B Ga N and P heteroatoms have been prepared., The ring is formed by a Lewis acid-base interaction between the gallium alkyl and the nitrogen base ends of the chain. A major feature of Group 13 organometal chemistry remains the search for interesting semiconductors and easy methods for the preparation of these materials. Amongst systems studied are thin films of Tl,O formed from TlCp;,’ GaN precursors;26 indium sulfide films; organoindium amine compounds of potential interest in MOVPE;28 formation of high quality epitaxial GaAs layers using dimethylamine gallane;,’ GaInP 1a~ex-s;~’ InP;,’ and the potential GaP precursor [C12GaP(SiMe3),],.32 There have been useful reviews concerning coordination compounds of aluminium as precursors to AlN,, and the marketplace application of GaAs., An interesting observation concerning the use of the group 13-15 semiconduc- tor GaAs is that VLSI (very large scale integrated) GaAs chips containing up to 50 OOO logic gates are now being fabricated.2 Coordination Chemistry The X-ray crystal structure of [A1C1,(NH3),][A1C1,(NH3),] shows that the alumin- iums are octahedrally coordinated in both the anion and the cation but that in + [AIClz(NH,),] the octahedra are elongated along the C1-A1-CI axis whereas they are compressed along the N-Al-N axis of the anion [AlCl,(NH,),]-.35 New hexadentate highly flexible chelating ligands (N303) based on l,l,l-tri(((2‘- hydroxy-benzy1)amino)methyl)ethanehave been prepared and their complexes with Al Ga and In synthesized and analysed by X-ray ~rystallography.~~ These amine phenols were prepared by KBH reduction of the Schiff bases formed from condensation of 1,l,l-tris(2-amino-methyl)ethanewith three equivalents of various salicylaldeh ydes.GaCl reacts with the tris-pyrazoyl borate ligand [HB(3,5-Me2pz),]- (= L*) or with the tetrakis-pyrazolyl borate anion [B(3,5,-Me,pz),] -( = L* -) ligand to form the stable salt [L,*Ga][GaCl,].37 In this compound the gallium is hexacoordinate and rather unreactive. Some related pyrazoyl borate compounds containing methyl gallium were also discovered namely L*GaMeCl L*GaMe, and LT-GaMe.These compounds all show fluxional NMR behaviour of the pyrazoyl borates and of the methyls when in solution. X-Ray crystal structure determinations were carried ” W. Uhl A. Vester and W. Hiller J. Organomet. Chem. 1993 443 9. 24 K.M. Webb and N. E. Miller J. Organomet. Chem. 1993 460,1. 25 P. Zanella G. Rossetto S. Sitran,and D. Ferro Eur. J. Solid State Inorg. Chem. 1992,29 (Supplement) 181. ’‘ M. J. Almond C. E. Jenkins and D. A. Rice J. Organomet. Chem. 1993 443 137. ” A.N. MacInnes M. B. Power A. F. Hepp and A. R. Barron J. Organomet. Chem. 1993 449 95. H. Schumann T. D. Seuss and H. Hemling Eur. J. Solid State Inorg. Chem. 1992 29 (Supplement) 81. 29 E. Malocsay V. Sundaram L. Fraas and A.Melas J. Cryst. Growth 1992 124 76. 30 R. Hovel W. Brysch N. Neumann K. Heime and L. Pohl J. Cryst. Growth 1992 124 106. 31 O.T. Beachey S.H. L. Chao M. R. Churchill and C. H. Lake Organometallics 1993 12 3992. 32 R. L. Wells M. F. Self A. T. McPhail S. R. Aubuchon R. C. Woudenberg and J. P. Jasinski Organometal-lics 1993 12 2832. 33 F.C. Sauls and L. V. Interrante Coord. Chem. Rev. 1993 128 193. 34 P.R. Jay Can. J. Phys. 1992 70 943. ’’ H. Jacobs and B. Nocker Z. Anorg. Allg. Chem. 1993 6 73. 36 S. Liu E. Wong V. Karunaratne S.J. Rettig and C. Orvig Inorg. Chem. 1993 32 1756. 37 D. L. Refer and Y. Ding Organometallics 1993 12 4485. Al Gu In and T1 29 The X-ray crystal structure of ~(octaethyloxophlorin)In111]2 shows that it is a dimer with the two macrocycles 3.25 A apart and with links through the rneso oxygen^.,^ The porphyrin-like macrocycles are only slightly distorted.Novel cobalt-aluminium cofacial porphyrins (DP)CoAl(OR) [DP4-is the tetra-anion of diporphyrin bipheny- lene (DPB) or diporphyrin anthracene; R = Me Et or benzyl] have been described.,' Mass UV-VIS IR ESR and 'H NMR spectra were all reported and the X-ray crystal structure of (DPB)CoAl(OEt) was determined. This is the first crystal structure of a heterobimetallic cofacial diporphyrin; it is unlikely that there is any appreciable metal-metal interaction with the Co-A1 distance at 4.370(1) A. The compounds show unusually large 'H NMR paramagnetic shifts for the protons on the axial ligands bound to the aluminiums.It was suggested that this arises from a through space (or dipolar) interaction with the paramagnetic cobalt(I1). The X-ray crystal structure of thallium(II1) rneso-tetraphenylporphyrin acetate shows that the acetate group is coordinated as a bidentate chelate.40 Tris complexes of the ligand 1-ethyl-3-hydroxy-2-methylpyridin-4-one with alumin- ium and gallium have been characterized.,' The pendent arm macrocycles 1,4,7- (triacetat0)- 1,4,7-triazacyclononane and 1,4,7-tris(2-mercaptoethyl)-l,4,7-triaza-cyclononane form (fuc-N,O,)Al and (fuc-N,S,)In hexadentate complexes. The average A1-0 and In-S bond distances were 1.846 8,and 2.397 A re~pectively.~~ The ligand 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) forms complexes M(taci)i + with AlI'I Ga"' and Tl"1.43 The metal coordination spheres change in a textbook fashion namely AlO, GaN,O, and TlN,.Tl(taci)+ was also observed.43 The oligomeric behaviour of alumatrane [Al(OCH,CH,),N] has been reinvestigated by mass spectra and by 27Al NMR and the presence of dimers and tetramers inferred.44 '51n NMR studies were reported for indium(xi1) halides in hexamethylphosphor- amide.InX (X = Br I) mixed anions 1nBr4-Jn [InCl,(hmpa),] and [(hmpa),I,In]I were observed and an X-ray crystal structure determination of the latter complex has been carried In a subsequent publication by this group of workers NCS- and NO complexes were observed by '"In NMR and mixed halide-pseudohalide species observed. The detection of N-bonded [In(NCS)J3 -and [In(N0,),I3-using 14N NMR (for the first time) was reported.A unique four- to six-coordination equilibrium was observed between these and tetracoordinate anions such as [In(NCS),] -.46 In another NMR study 205Tl 2D NMR (EXSY) and 13C NMR have been used to study cyanide exchanges in aqueous solutions containing T1(' ,CN) and [Tl('3CN),]-. The very large (up to 8 kHz) 205Tl-'3C spin-spin coupling constants enabled six exchanging sites for 13C and nine exchanging sites for "'Tl to be ob~erved.,~ 38 A. L. Balch B.C. Noll M. M. Olmstead and S. M. Reid J. Chem. Soc. Chem. Commun. 1993 1088. 39 R. Guilard M.A. Lopez A. Tabard I>. Richard C. Lecomte S. Brandes J.E. Hutchinson and J. P. Collman J. Am. Chem. Soc. 1993 114 9877. 40 S-C. Suen W-B. Lee F-E. Hong T-T. Jong J-H.Chen and L-P. Hwang Polyhedron 1992 11 3025. 41 G.Y. Xiao D. van der Helm R.C. Hider and P.S. Dobbin J. Chem. Soc. Dalton Trans. 1992 3265. 42 U. Bossek D. Hanke K. Wieghardt and B. Nuber Polyhedron 1993 12 1. 43 K. Hegetschweiler M. Ghisletta T. F. Fassler R. Nesper H. W. Schmalle and G.Rihs Inorg. Chem. 1993 32 2032. 44 J. Pinkas and J. G. Verkade Inorg. Chew. 1993 32 2711. 45 M. A. Malyarick A. B. Ilyuhin and S. 1'. Petrosyants Polyhedron 1993 12 2403. 46 M. A. Malyarick and S. P. Petrosyants Inorg. Chem. 1993 32 2265. 47 G. Batta I. Banyai and J. Glaser J. Am. Chem. Soc. 1993 115 6782. 30 J. P. Maher An intriguing and very stable tri-radical gallium complex has been characterized by means of X-ray structural ESR and magnetic susceptibility measurements namely tris(3,5-di-t-butyl-1,2-semibenzoquinonate) gallium(m) [(tbsq-),Gal.The semi-quinonate ligands are bidentate giving a distorted octahedral GaO coordination to the gallium. The triradical shows both quartet and doublet states as expected. These were observed in the frozen solution ESR spectra and their assignment supported by spectra simulation and by means of variable temperature magnetic susceptibility measure- ments. At higher temperatures the latter measurements show that another doublet state is populated giving rise to the species [(tbsq-)(tbc)(tbq)Ga] i.e.two of the electrons are paired {tbc = 3,5-di-t-butyl-cathecolate; tbq = 3,5-di-t-butyl-quinone}. Reaction of the triradical complex with pyridine generates another monoradical species [(tb~q.)(tbc)(py)~Ga].~~ The reaction of AlCl with quinones leads to paramagnetic materials which have also been studied by ESR and by ENDOR spectros~opy.~~ Kinetic measurements have been reported for the group 13 metals.The formation of the aluminium(II1) monocarboxylates (formate acetate chloroacetate and benzoate) have been studied by stopped-flow measurements. The inner sphere rate and the equilibrium constants for these substitutions depend upon the ligand. A linear free energy relation was observed between the rate and equilibrium constants for the carboxylic acids. The redox reaction of Tl"'-aqua and -chloride species with 1-ascorbic acid has the following decreasing rate constant order [T1OHl2+ > T13+ > [T1C1l2+> [TlCl,] + > TlCl > [TlCl,] -.Reduction of Tl"' by hydrogen peroxide in 1.O mol dm- perchloric acid is first order with respect to T1"' and second order in hydrogen peroxide. Both H+ and C1- show negative rate catalysis but for Br- catalysis is positive. A radical-based mechanism was proposed. The reactivity of the various bromothallium(II1) species follows the order [T1Brl2+ < [TlBr,]' > TIBr < [TlBr,]-. A very complex rate law dependence for these kinetics was observed.52 3 Chalcogenide Compounds The crystal structures of the mixed valence compounds In$ and [Sn,,,(In,S,)] have been re-examined; this is important since In,S is the only example of a monovalent indium-sulfur complex. It was shown that the two compounds are isotypic and that the tin compound is a variation of the In$ compound in which the In+ ions are substituted by up to 50% with Sn2+ 53 The synthesis of new homoleptic indium(II1) polysulfide complexes [Ph,P],[In2S2,] (1) and [PPh,]2([In,S14]o~,[InS16]o,5} (2) has been described and their X-ray crystal structures determined.54 The indium-containing anion in (1) consists of trigonai 48 A.Ozarowski B. R. Mcgarvey A. El-Haded Z.G. Tian D. G. Tuck D.J. Krovich and G.C. DeFotis Inorg. Chem. 1993 32 841. 49 A. V. Astashkin R. I. Samoilova M. Zdravkova and N. Iordanov J. Struct. Chem. (Engl. Transl.) 1992 33 605. A. Pohlmeier U. Thesing and W. Knoche Ber. Bunsenges. Phys. Chem. 1993 97 10. 51 J. Agrawal S. Nahar S.K. Mishra and P.D. Sharma J.Phys. Org. Chem. 1993 6 179.52 M.S. P. Rao A. R. M. Rao and P. Vani React. Kinet. Catal. Lett. 1992 48. 519; M. S. P. Rao A. R. M. Rao R. Kalavathi T. S. Rao and P. Vani J. Chem. SOC. Dalton Trans. 1993 2283. 53 H. J. Deiseroth H. Pfeifer and A. Stupperich Z. Kristallogr. 1993 207 45. 54 S.S. Dhingra and M. G. Kanatzidis Inorg. Chem. 1993 32 3300. Al Ga In and TI 31 bipyramidal coordinated In"'; each indium atom is coordinated by two bidentate chelate polysulfide Si-and Si-units forming a [In(S,)(S,)]- unit and an S;-chain links two of these into a dimer. In (2) the S-14 and S-16 anion groups have equal occupancy and contain tetrahedral In"' centres. The indium atoms are bridged by an S2-and by an Si-moiety to form an eight-membered [In,S(S5)I2+ ring core which the authors describe as having an extreme cradle configuration.There are two remaining coordination sites and in these the indium atoms are coordinated by an S2-chelate on one side and (in random disorder) by a S:-or Si-on the other. In a related paper the same authors have reported their investigations into the polyselenide chemistry of In"' and identified the three new complex anions [In,(Se4)(Se5)l4- [In2(Se,)(Se,)12 -,and [In3(Se,)(Se4)l3- .55 Single crystal X-ray diffraction studies showed that all three contain the same tetra-negative anion with the In"' centres in trigonal bipyramidal coordination and each In"' bidentate chelated by two Sei- ligands in the form of an [In(Se,),]- unit which is then bridged by an Seg- chain of seleniums. This is somewhat reminiscent of the previous sulfur complex (1) described above.The binuclear anion [In,Se2(Se4),12 -was crystallized with both [Pr,N] and + + [(Ph,P),N] cations and X-ray crystal structures determined. In the anion [1n,Se,(Se4),l2 -indium ions are tetrahedrally coordinated and bridged by two Se2 -ions to form a planar [In,Se,12+ core with an inversion centre at the middle of the In-In vector (= 3.336(2)A). The two remaining coordination sites on each indium atom are occupied by Sei- bidentate chelates. The trinuclear ion [M,Se,(Se,),13 -(M = In T1)was formed. The M3+ions are tetrahedrally coordinated by a chelate Se:- ligand and bridged to other M3+ centres by Se2- ions so forming a six-membered [M,Se,13+ core. GaCGaCl,] reacts in toluene bith elemental sulfur to give GaSCl and subsequent addition of pyridine then gives the adduct [GaSCl-py] which has a boat-shaped gallium-sulfur ring str~cture.'~ Indium thiolate and selenolate complexes [S(2,4,6-Bu'C6H2),In] and [(Se(2,4,6- Bu'C,H,),In] both show a trigonal planar coordination of the indium atom.57 4 Zeolitic and Clay Materials A large portion of the literature which concerns aluminium chemistry involves various uses for alumina and related aluminium oxide compounds particularly molecular sieve and clay minerals.Aluminium-pillared clays (montmorillonites) can be prepared and used as catalyst supports for example by supporting nickel sulfide catalysts in thiophene hydrodesulf~rization.~~ Gallium and aluminium clays and zeolites can be used in the dehydrocyclodimerization of propane.59 Acid-activated montmorillonite clays can be used to adsorb ch1orophylk6' Aluminophosphate molecular sieves described as consisting of 'hydrated triple crankshaft chains' have been prepared and characterized.The AlPO hydrate is 55 S. S. Dhingra and M. G. Kanatzidis Inorg. Chem. 1993 32 1350. 56 J. Oshita A. Schier and H. Schmidbaur J. Chem. SOC.,Dalton Trans. 1992 3561. 57 K. Ruhlandt-Senge and P. P. Power Inorg. Chem. 1993 32 3478. 58 J.T. Kloprogge W. J. J. Welters E. Boo) V. H. J. Debeer R. A. Vansanten J. W. Geus,and J. B. H. Jansen Appl. Catal. (General) 1993 97,77. 59 S. M. Bradley and R. A. Kydd J. Catal. 1993 142 448. 6o R. Moyaya W. Jones M. E. Davies and M. E. Whittle J. Muter. Chem. 1993 3 381.32 J. P. Maher constructed exclusively from a hydrated chain building unit which also builds the 18-ring VP 15 structure and has one-dimensional channels circumscribed by highly elliptical rings consisting of ten oxygen atoms.61 The hydrothermal synthesis and X-ray crystal structure of [H,NCH2CH,NH,][In,(HP04)4] has been described. This is the first organically-templated indium phosphate and its lattice contains a novel octahedral-tetrahedral framework.62 Room temperature crystallization of an aqueous NMe40H/A120,/Si0 solution gave large crystals of the novel hydrate phase [NMe4],[A1,Si8 -,O -,(OH) + ,] .44H20(x = 3 to 4). The X-ray crystal structure of this zeolite-type clathrate hydrate was determined. The hydrate is a further member of a recently discovered series of clathrates with mixed tetrahedral networks which provide a structuralxhemical link between zeolite and clathrate hydrate types of host-guest compound.In the structure the disordered cationic guest NMe is enclosed in the large polyhedral voids of the host framework whilst smaller cages in the structure are empty.63 5 Bioinorganic Chemistry Aluminium(II1) or the other group 13 metal ions have no known beneficial or essential biochemical functions. However the possible connection between aluminium ions and Alzheimer's disease encourages studies of how Al"' may be coordinated to and interfere with biochemical mechanisms and how it might move among possible coordination sites in vivo. In addition Ga and In have radiopharmaceutical uses.The binding of Al"' to ovotransferrin proteins has been investigated by means of 3C and 27Al NMR. The study revealed a clear difference between the N-terminal and C-sites of the protein in the binding of aluminium(II1). Carbonate and oxalate ions affect the binding so that in the presence of carbonate the N-terminal site binds Al"' with higher affinity than does the C-site. Oxalate reverses the ~pecificity.~~ A possible source of aluminium for ingestion is the metal of an aluminium teapot! 27AlNMR has been used to examine aluminium complexes in aqueous tea extract. The model chelating ligands studied were catechol pyrogallol catechin kojic acid protocatechuic acid ascorbic acid (who likes lemon tea then?) and salicylic acid. All of these showed broad 27Al resonances in the 8-36ppm region of the spectrum.From this the [A1(C2O4)l3- ion a mixed oxalate and a malate complex were identified in the tea infusion^.^^ Another possible route for dispersal in vivo could be via administered drugs. Aluminium(m) can form complexes with adriamycin and its analogues. The main complex at pH > 5 is a tetrahedral species in which the metal ion is coordinated to the ligand through two anthracycline oxygens and two OH groups. At pH > 8.5 the formation of [Al(OH),] -prevents adriamycin coordination.66 Whilst gallium(II1) and indium(Ir1) have no known bioinorganic chemical functions they may be useful in other capacities. The complexes tris(tropo1onato)-gallium(1Ir) 61 H-X. Li M. E. Davis J. B. Higgins and R.M. Dessau J. Chem. SOC.,Chem. Commun. 1993 403. S.S. Dhingra and R.C. Haushalter J. Chem. SOC. Chem. Commun. 1993 1665. 63 M. Grube W. Wiebcke J. Felsche and G. Engelhardt Z. Anorg. Allg. Chem. 1993 619 1098. 64 J. M. Aramini and H. J. Vogel J. Am. Chem. SOC. 1993 115 245. " S.N. Mhatre R.K. Iyer and P. N. Moorthy Magn. Reson. Chem. 1993 31 169. 66 E. Pereira M. M. L. Fiallo A. Gamier-Suillerot,T. Kiss and H. Kozlowski J. Chem. SOC.,Dalton Trans. 1993 455. Al Ga In and T1 33 and -indium(m) may be prepared in water from tropolone and the metal(m) nitrate. Their X-ray crystal structures were determined and compared with corresponding A~(III) and Fe(m) complexes. The coordination parameters of the tropolonate ligand to the metals reflected the inflexibility of the ligand.The complexes are lipid soluble and may be of radiopharmaceutical interest.67 Aluminium(I1I) and gallium(II1) form complexes with 2-(2'-hydroxyphenyl)-2-benz-oxazole (hbo) [Ga(hbo),] [Ga(hbo),(acetate)] and [Al(p-OH)(hbo),],. X-Ray crystallography and 'H I3C and 27AlNMR were used to examine the structures in the solid state and in solution. The aluminium complex is a relatively rare example of a crystallographically characterized bis(p-hydroxo)-bridged dimer. The ligand has some analogies with various in uiuo metalloenzyme binding sites.68 6 Hydrides Frozen noble gas matrices observed by means of FTIR spectroscopy provide a powerful tool for the identification of normally unstable molecules. Broad-band photolysis of a solid noble gas matrix containing aluminium atoms and dihydrogen gives the planar monomeric AIH molecule.69 Similarly the reactions of gallium with dihydrogen in the gas-phase followed by matrix isolation in argon gives GaH and GaH [H-Ga-H = 136" & 5"].Ga reacts with H to form Ga,(p-H) which is converted photo-reversibly into H-Ga-Ga-H .70 Crystalline adducts of aluminium trihydride with tetrahydrofuran of composition [AlH,.thfJ and [AlH,(thf),] have been prepared from solutions of alane in THF and from the reaction of [Me,.A1HJ2 with THF. Their X-ray crystal structures have been determined. ' The reaction between [AlH,(NMe,)] or [AlH,Cl(NMe,)] and the sterically crowded phenol C6H,(2,6-Bui,4-Me)(OH) (R'OH) gives [AlH,(OR' )(NMe,)] (as monomers and dimers) and [AlHCl(OR' )(NMe,)] respectively.Further reactions of these materials to form a number of aryl-alkoxides and hydrides were studied.72 [AlH,(NMe,)] also reacts with 1,2-bis(dimethyIphosphino)ethane to give [Me,N.AlH,],.dmpe. This complex has N- and P-donor groups in apical trigonal bipyramidal positions. [H,Al*(N-methylmorpholine)] and [H,Al(quinuclidine)] were prepared from LiAIH and the appropriate amines the X-ray crystal structures of these were determined.73 7 Metal-Metal Bonded Compounds The preparation of tetrasubstituted di-aluminium compounds only became possible with the advent of very highly sterically shielded ligands. Thus tetrakisCbis(trimethy1- si1yl)methyll-dialuminium ( =R,A1-AIR,) is remarkably stable shows an Al" oxida-67 F.Nepveu J. Jasanada and L. Walz Inorg. Chim. Acta 1993 211 141. 68 H. R. Hoveyda S.J. Rettig and C. Orvig Inorg. Chem. 1993 32 4909. 69 F. A. Kurth R.A. Eberlein H. Schnockel A. J. Downs and C. R. Pulman J. Chem. SOC.,Chem. Commun. 1993 1302. 'O Z. L. Xiao R. H. Hauge and J. L. Margrave Inorg. Chem. 1993 32 642. 71 I.B. Gorrell P. B. Hitchcock and J.D Smith J. Chem. SOC. Chem. Commun. 1993 189. 72 M. D. Healy M. R. Mason P. W. Gravelle S.G. Bott and A. R. Barron J.Chem. SOC.,Dalton Trans. 1993 441. 73 J. L. Atwood K. W. Butz M. G. Gardiner C. Jones G. A. Koutsantonis C. L. Raston and K. D. Robinson Inorg. Chem. 1993 32 3482. 34 J. P. Maher tion state and an AI-A1 bond.74 The dialane reacts with Bu’Li in the presence of tetramethylenediamine (tmeda) to form the hydridoaluminate [R,Al-AlHR,].Treat-ment of R,Al-AlR with MeLi gives [R,Al-AlMeR,]-. The compounds do not have bridged Al-A1 bonds but a tetracoordinate aluminium bonded to a trigonal coordinate aluminium. The AI-A1 bond length in the hydrido derivative [2.667(3) A] is the same as in the dialane. In the methyl derivative the Al-A1 bond is slightly lengthened [2.752(3) A].75 Lithium reduction ofdialane was reported to give a salt which after the addition of tmeda gave a radical anion [R,AI-AIR,]- where the Al-C bonds are longer by 0.06 A and the A1-A1 bond shorter by 0.13 A. Molecular orbital calculations indicate that the Al-A1 bond is stabilized by an extra one-electron n-b~nd.~~ Similarly reduction of [(Trip),GaGa(Trip),] (Trip = 2,4,6-trisPr‘(C,H,)) also generates a radical anion with a Ga-Ga n-bond which is also shortened by 0.17 8 to 2.343(2) The ligand 2,4,6-tris(trifluoromethyl)phenylwill also stabilize Ga-Ga and In-In bonds.78 Clusters of group 13 metals with metal-metal bonds have been discovered in several different situations.Thus a cryochemically prepared solution of GaCl in tol-uene/diethyl ether gives a molecular compound [((Et,0),C1Ga)Ga{GaC12(Et,0))3] with a tetrahedral Ga unit in which each Ga is tetrahedrally coordinated. The central gallium is surrounded by the four gallium atoms bearing the diethyl ether and chloride moieties.79 Another technique for the preparation of group 13 metal clusters involves fusing alkali metal mixtures with the metal followed by slow cooling of the melt.Thus [M,Na,,In,,] (M = K Rb Cs) compounds were obtained by slow cooling of the appropriate fused mixture of the elements in a tantalum container. The indium cluster consist of closo-In, icosahedra of T symmetry plus arachno-In, of D, and D6d hexagonal antiprisms (described as ‘drums’) with 12 exo In-In bonds about each cluster. Finally there is continuing interest in the formation of various transition metal carbonyl clusters incorporating group 13 metals (see for example references 8 1 82). 8 Thallium-based Superconductors Research into high T thallium-based superconductors is perhaps a little less brisk than a couple of years ago. However research into new materials and methods of improved preparation and analysis as well as an improved understanding of the structures are all represented in 1993 publications.Copper oxycarbonates can have a layered perovskite structure which facilitates the synthesis of a new series of high T superconductors. The best of these oxycarbonate 74 W. Uhl Angew. Chem. Int. Ed. Engl. 1993 32 1386. ’’ W. Uhl and A. Vester Chem. Ber. 1993 126 941. ’‘ C. Pluta K. R. Porschke C. Kruger and K. Hildenbrand Angew. Chern. Int. Ed. Engl. 1993 32 388. 77 X. He R. A. Bartlett M. M. Olmstead K. Ruhlandt-Senge B. E. Sturgeon and P. P. Power Angew. Chem. Int. Ed. Engl. 1993 32 717. R. D. Schluter A. H. Cowley D. A. Atwood R. A. Jones M. R. Bond and C. J. Carrano J. Am. Chem.Soc. 1993 115 2070. 79 D. Loos H. Schnockel and D. Fenske Angew.Chem. Int. Ed. EngI.. 1993 32. 1059. 8o S.C. Sevov and J. D. Corbett Inorg. Chem. 1993 32 1612. M. Schollenberger B. Nuber M. L. Ziegler and E. Hey-Hawkins J. Organomet. Chern. 1993 460 55. C-C. Lin G. Kong H. Cho and B. R. Whittlesey Inorg. Chern. 1993 32 2705. Al Ga In and TI 35 superconductors is T1,~,Pb,~,Sr,Cu2(C0,)07 which has a T of 70 K.83 A new family of thallium cuprates TlSr -,Ln,Cu207 (Ln = Pr Nd Y) related to the hypothetical compound TlSr,Cu,O have T,s up to 95K for 0.75 > x > 0.5. Of these T1 -,Pb,Sr,-,NdxCu207 (y = 0.2 x = 0.5) had the highest T of 95 K.84 Thin films of T1Ba2Ca2Cu,0g superconductor materials with high T (1 17 K) can be prepared on a MgO [loo] surface by a combination of laser ablation from a stoichiometric Ba,Ca,Cu,O target and the thermal evaporation of thallium(1) oxide.8s A new wet chemical method based on the redox chemistry of the Cu'/Cu" couple and potentiostatic electrolysis has been used for the determination of the high metal valences in thallium cuprates.The method determines the sum of the extra oxidation states of Cu"' and T1"' above those of Cu" and T1' and enables measurement of the oxygen content of the sample.g6 The stability of the phases 2223 and 2212 for the superconductor T1,-,Ba2Ca2Cu,0,,-x (0.35 < y < 0.75) and theeffect upon T have been examined particularly with respect to the temperature firing conditions. X-Ray diffraction coupled with high-resolution electron microscopy measurements gave a structure model in which double rock-salt layers of [(TlO)(SrO)]-intergrow with single perovskite layers [SrCuO,] and layers of carbonate groups according to the formulation [(~ro)(Tlo.5~b0.5°)]R,,ck salt~~SrCU03~2~Perovsk~*e~srco3~~g7 9 Thallium(1) Irregular coordination about the T1' ion in an X-ray crystal structure determination for T12Se04 may be due to the stereochemical activity of the thallium lone pair. This structure is similar to that of T12Cr04.g8 Ab initio Quantum mechanical calculations of the molecular properties of thallium(1) and (111) halides (taking into account relativistic and electron-correlation effects) show good agreement with experimental results for bond distances and dipole moments. Interestingly a trigonal planar structure for the gas-phase species TlI is preferred to the T11(13)bent structure.The free energy difference calculated between these forms 95 kJ mol -',is considerableg9 Thallium maintains its reputation for providing compounds with extreme properties in that Tl,BX4 (B = V Nb Ta; X = S Se) compounds have been shown to exhibit the strongest piezoelectric effects known.g0 A new thallium mineral fangite Tl,AsS, has been discovered in a gold mine sulfide ore stockpile in Tooele County Utah. The mineral has a deep red to maroon colour with an orange streak it is translucent but tarnishes to a nearly metallic lustre. An X-ray single crystal structure determination showed tetrahedral As-coordination and TI in trigonal bipyramidal coordination with sulfur.' Following work on other group 13 trivalent chal~ogenides,~~*~~ the synthesis of the 83 M.Huve C. Michel A. Maignan M. Hervieu C. Martin and B. Raveau Physica C 1993 205 219; B. Raveau M. Huve A. Maignan M. Hervieu C. Michel B. Domenges and C. Martin ibid. 1993,209 163. R4 V. Manivannan N. Rangavittal J. Gopalakrishnan and C. N. R. Rao Physica C 1993 208 253. 85 A. Piehler R. Low J. Betz R. Schonberger and K.F. Renk J. Appl. Phys. 1993 74 6437. 86 M. Karppinen A. Fukuoka T. Kaneko and Y. Yarnauchi Superconduct. Sci. Techn. 1993 6 265. 87 K. S. Nanjundaswarny A. Manthiram and J. B. Goodenough Physica C 1993 207 339. 8R J. Fabry and T. Breczewski Acta Crystallogr. Sect. C 1993 49 1724. 89 P. Schwerdtfeger and J. Ischtwan J. Cornputat. Chem. 1993 14 913. 90 H. Maleki and P. Buck 2.Kristallogr 1993 207 103. 91 J. R. Wilson P. K. Sengupta P. D. Robinson and A. J. Criddle Am. Mineral. 1993 78 1096. J. P. Maher first thallium(1) polysulfides have been described (the Tl"' compounds are not stable due to the high redox potential of Tl"'). All of the compounds whose X-ray crystal structures were measured contained the same structural unit namely [Tl,(S,),]* -. In this anion the two T1' trigonal pyramidal centres are each chelated by a tetrasulfide ligand whilst the third coordination site is bonded to a terminal sulfur of another TIS unit and forms a dimer. This gives a new condensed inorganic ring system with a central strictly planar rhombic unit and two five-membered TlS rings in an envelope configuration .92 Several new T1' complexes have been prepared :thallium(1)-2-pyridyl-cyanoxime~~ a volatile chelate (2,2,6,6-tetramethyl-3,5-heptanedionato)thallium(1),~~ (N,N-diethyl-N'-benzoylselenureato) thallium(~),~' and a metallo-ligand with a bicoordinate angular T1' [Pt2Tl(p3-S),(PPh,),]X (X = NO, PF,) described as having a mexican-hat like str~cture.~~ Thallium(~)has been incorporated into various crown ether complexing agents e.g.[T1(12-~rown-4)],.~~ A thallium atom is found in close (2.897(2)A) proximity to a palladium(I1) in [T~(crown-P2)Pd(CN),][PF6]~CHCl3, where TI-Pd bonding may also exist. However in a bridged tetra-acetate Pd"/TI"' complex Pd(m-O,CMe),Tl(O,CMe) a short TI-Pd distance is also observed (2.702A) but it was considered that this does not represent any appreciable TI-Pd bonding.98 Other crown complexes are the thallium-rich compound [(TI( 18-~rown-6)),CuBr~][TlBr,]~,~~ and dibenzo-22-crown-6.loo It is appropriate to end on yet another record for thallium chemistry! The equilibria dynamics and structures of [Tl(edta)X2 -1 (X = halide psuedohalide) have been studied at length by "'Tl "N 13C and 'H NMR and the coupling constant J 205Tl-' 3C for the complex [Tl(edta)CN] -found to be 10479 30 Hz. This indicates a remarkably strong TI-C bond. An X-ray crystallographic determination of the structure of Na2[Tl(edta)CN]-3H2O showed that the thallium is coordinated to both the edta and the cyanide in a seven-coordinate geometry configuration. lo' 92 S.S. Dhingra and M. G. Kanatzidis Inorg. Chem.1993 32 2298. 93 N.N. Gerasimchuk L. Nagy H.G. Schmidt M. Noltenmeyer R. Bohra and H.W. Roesky Z. Naturforsch. Teil B 1992 47 1741. 94 R. Amano and Y. Shiokawa Inorg. Chim. Acta 1993 203 9. 95 W. Bensch and M. Schuster Z. Anorg. Allg. Chem. 1993 619 1689. 96 M. Zhou Y. Xu L.L. Koh K. F. Mok P-H. Leung and T.S. Andy Hor Inorg. Chem. 1993,32 1875. 97 H. Vonarnim and K. Dehnicke Z. Naturforsch Teil B 1993 48 1331. 9B A. L. Balch B.J. Davis E.Y. Fung and M. M. Olstead Inorg. Chim. Acta 1993 212 149. 99 I. A. Kahwa D. Miller M. Mitchel and F. R. Fronczek Acta Crystullogr. Sect. C 1993 49 320. 100 M. Fujiwara T. Matsuchita. Y. Yamashoji M. Tanaka. and M. Ouchi T. Hakushi. Polyhedron. 1993,12 1239. J. Blixt J. Glaser P. Solymosi and I. Toth Inorg. Chem. 1992 31 5288.

ISSN:0260-1818    

DOI:10.1039/IC9939000025

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

4 C,Si Ge Sn and Pb By D.A. ARMITAGE Department of Chemistry King's College Strand London WC2R 2LS UK This review covers the literature for 1993. The rapidly developing chemistry of fullerenes has been covered in a book,' and reviews have described their patterns of addition- organic- oxidation- and halogenation-chemistry and their various haptici- ties.2 The topic has been briefly o~erviewed.~ Fulgurite a phenocryst-rich quartz latite mineral from Sheep Mountain Colorado has been shown to contain c60and C70 formed through lightening strikes. It is thought that the carbon is provided by the fruits of the forest floor. Both c60 and C70 also result from the collisional heating of carbon rings in the gas-phase and from the direct vaporization of carbon in focused ~unlight.~ c60 is formed in discharges through polycyclic aromatic hydrocarbons and the pyrolysis of naphthalene at 1000"C.6 Both c60 and C70 occur in flames while precursors to c60 include appropriately trisubstituted triphenylene and triindenotriphenylene leading to sumanene C ,HI2.7 Cyclo[n]carbons result from polyyne bridged cyclobutenediones which lose CO ; cyclo[30]carbon pyrolyses to c60 but for n = 18 or 24 C70 predominates in the mass spectrum.* Huckel calculations support the tetrahedral isomer of c28 and suggest stability for C; C28H4 U@C2, and c24x\;'4.Topological resonance energies for the anions of c60 suggest they retain their aromatic character while the tetra-anions of c28,C36 and C, should be highly aromatic and form stable endohedral U4+derivatives.' An enumeration of the chiral isomers of substituted fullerenes suggests that there are none Fullerenes New Horizon for the Chemistry Physics and Astrophysics of Carbon'.ed. H. W. Kroto and D. R. M. Walton Cambridge Universitj Press 1993. ' R.Taylor Phil. Trans. R. SOC.London A 1993,343,87; R. Taylor and D. R. M. Walton Nature 1993,363 685; G. P. Miller Chem. Ind. 1993,226;V. I. Sokolov Dokl. Akad. Nauk 1992,326,647 (Chem.Ahstr. 1993 118 124592). A. Hirsch Angew. Chem. Int. Ed. Engl. 1993 32 1138; R. F. Curl Nature 1993 363 14; P. Ball Nature 1993 361 297. T. K. Daly P. R. Buseck P. Williams and C. F. Lewis Science 1993 259 1599. G. von Helden N. G. Gotts and M.T. Bowers Nature 1993 363 60; L. P. F. Chibante A. Thess J. M. Alford M.D. Diener and R.E. Smalley,J. Phys. Chem. 1993,97,8696;C. L. Fields J. R. Pitts M. J. Hale C. Bingham A. Lewandowski and D. E. King ibid. 1993 97 8701. M. T. Beck Z. Dinya S. Keki and L. Papp Tedrahedron 1993 49 285; R. Taylor G. J. Langley. H. W. Kroto and D. R.M. Walton Nature 1993 366,728. ' C. J. Pope J. A. Marr and J. B. Howard .I.Phys. Chem. 1993,97 11 001 ;R.Faust and K. P. C. Vollhardt J. Chem. SOC.,Chem. Commun. 1993,1471;(2. N. Sastry E. D. Jemmis G. Mehta,and S. R.Shah,J. Chem. Soc. Perkin Trans. 2 1993 1867. S. W. McElvany M. M. Ross N. S. Goroff and F. Diederich Science 1993 259 1594. P. W. Fowler S.J. Austin and J. P. B. Sandall J. Chem. Soc. Perkin Trans. 2 1993,795; J.4. Aihara and H. Hosoya Bull. Chem. Soc. Jpn. 1993 66. 1955. 37 D.A.Armitage for monosubstituted C (n = 20 24 28 30 36 and 60) though they are possible for other values of n and that all appropriately disubstituted fullerenes exhibit chirality. The 13C NMR signals have been enumerated for all fullerenes from C, to C,,.'' Calculations suggest the D isomer of C, to be 43 kcal mol- more stable than that of the symmetry lowered T -+ D, isomer (due to partially filled HOMO and first order Jahn-Teller distortion).' ' Structural considerations and addition patterns to C, suggest that regioselective saturation of six double-bonds would lead to aromaticity in eight six-membered rings and this is observed in [(Et,P),Pt],C,,.' Geometric calculations suggest families of giant fullerenes C, in which for example C70xspecies show D, symmetry for x = 1,3,4,9,12,and 16,but for c4go (x = 7) a chiral pair of D symmetry is predicted.' Closed cages containing only boron and nitrogen can be constructed with six four-membered rings and a number of six-membered rings -polar six-membered rings being surrounded by alternate four- and six-membered rings.Their general formula is (BN), + ,,(n = 0-6) and they resemble progressively more extended accordions. l4 A phase diagram plot for c, suggests that it does not have a liquid-phase though others suspect one in a narrow range above 1800K.' Its solubility in hexane toluene and carbon disulfide is greatest at 280K for all three solvents; the latter is the best dissolving 7.9 mg ml- '. Solubility is three and four times greater in 1,2-dichloro- benzene and 1-methylnaphthalene.' The group additivity method predicts a gas- phase heat of formation of c, some 6% higher than the latest experimentally determined value.' HPLC separation of C76 C,, C,, and mixtures of c, to C,, suggest an isomeric mixture for C, from the NMR spectrum with the C," D, and C2" isomers in the ratio 52 30 18.For Cg4 13CNMR peaks are consistent with a D, and the D isomer together with minor amounts of D, and D, isomers. The retention time of Cg2 is inconsistent with those of the other fullerenes and suggests a C, structure that is polar (as C, is thought to be). C, co-eluted with C70H12 which is considered to have been reduced at three 6:6 bonds in naphthalene-like units adjacent to the two polar pentagons as a result of hydrogen abstraction from the hexane used in the elution.With increasing chemistry numbering 7r-bond order and addition pattern considerations have been addressed for C (n = 60 70 76 78 and 84).' Elevated temperature gel-permeation chromatography separates C,, and cyclic voltammetry reveals five reversible reduction waves but no oxidation ones. l9 Endohedral energies have been calculated for the noble gases and c6,. In the case of lo K. Balasubrarnanian J. Phys. Chem. 1993 97 6990 4647 and 8736. 'l J.R. Colt and G. E. Scuseria J. Phys. Chem. 1992 96 10 265. P.W. Fowler D.J. Collins and S. J. Austin J. Chem. SOC. Perkin Trans. 2 1993 275. l3 J.S. Rutherford Inorg. Chem. 1993 32 3579. l4 I. Silaghi-Dumistrescu I. Haiduc and D. B. Sowerby Inorg.Chem. 1993 32 3755. l5 M. H. J. Hagen E. J. Meijer G.C. A. M. Mooij. D. Frenkel and H. N. W. Lekkerkerker Nature. 1993,365 425; A. Cheng M. L. Klein and C. Caccarno Phys. Rev. Lett. 1993 71 1200. l6 R. S. Ruoff R. Malhotra D. L. Huestis D. S. Tse,and D. C. Lorents Nature 1993,362,140;W. A. Scrivens and J. M. Tour J. Chem. Soc. Chem. Commun. 1993 1207. l7 D. A. Armitage and C.W. Bird Tetrahedron Lett. 1993,34,5811; H. P. Diogo M. E. M. da Piedade T. J. S. Dennis J. P. Hare H. W. Kroto R. Taylor and D. R. M. Walton J. Chem. SOC.,Faraday Trans. 1993,89 3541. l8 R. Taylor G. J. Langley A.G. Avent T. J.S. Dennis H. W. Kroto and D. R. M. Walton J. Chem. Soc. Perkin Trans. 2 1993 1029; R. Taylor ihid.,1993 813. M.S. Meier T. F. Guarr J. P. Selegue and V.K. Vance J. Chem. Soc. Chem. Commun. 1993 63. C Si Ge Sn and Pb 39 He@C,, prepared under partial pressure of He heating releases 4He and ,He but only one 4He in every 880000 fullerene molecules. This release is thought to occur through a temporary cleavage of a C-C bond to provide a 'window' which then assists re-entry of other monatomic gases under pressure.20 Coorongite is a precursor of oil shales and occurs in the coastal lowlands of the Coorong district of South Australia. On pyrolysis in He the residues analyse for Ca@C as well as C, the endohedral derivatives being most common for n = 60 70 and 92 with prominent peaks for C, and c,36.21 The endohedral di-scandium fullerenes Sc,@C (n = 74 82 84) result from arc burning Sc,O,/graphite composite rods.La@C, results in high yield from Lac enriched composite carbon rods and shows five reversible waves by CV despite a formal charge of 3-on c,, the first giving the closed-shell species La@C; through pairing in the HOMO., Remarkably intercalation of Na,CsC, by ammonia increases the superconducting transition temperature T by about 20 K to 29.6 K but K3C60 which has a T of about 19K is not superconducting in the presence of ammonia.23 M,C,O (M = K, Cs, CsRb, RbCs, and KRbCs) species are readily prepared in liquid ammonia and superconductivity is achieved on heating to 375 "C for 1-2 days.24 Paraconductivity the anomalous increase in conductivity just above T, results from small transient regions of superconductivity. Three-dimensional paraconductivity is observed in K,C, and Rb,C,,., While Rb3(13C,,) shows an increase of 0.7K for T over Rb3(l2C,,) an intramolecular efTect is thought to account for the increase in T of 0.9 K for Rb,('3C,,),,,('2C60)0~5.26 ,'Rb NMR spectra show two tetrahedral and one octahedral site in Rb3C, at 440K but below 370K an additional tetrahedral resonance appears that may be due to placing Rb above a C ring of C,,3-.Orientational disordering in Na,RbC, may account for the low T of this superconductor which does not fit the relationship between T and lattice constant.27 c60 can be elegantly reduced using 1,2 or 3 moles of the 19-electron C,H,FeC,H to give the paramagnetic salts of the anions C60n- (n = 1 2 3)., These anions as benzoquinone 9,10-dihydroanthracene and 1,4-dicyanonaphthalene salts selectively debrominate with C& only reducing highly electron-withdrawing (BrCl,C) .29 Heats of formation of A,C, for A = Na K Rb cs are -28 -39 -40 and -47 kcal mol- respectively with all but Na of the metals reacting directly with C, at 2o L.Pang and F. Brisse J. Phys. Chem. 1993,97,8562;M. Saunders H. A. Jimenez-Vazquez R. J. Cross and R. J. Poreda Science 1993 259 1428. H. R. Rose I. G. Dance K. J. Fisher D. R. Smith G. D. Willett and M. A. Wilson J. Chem. Soc. Chem. Commun. 1993 941. 22 H. Shinohara H. Yamaguchi N. Hayashi H. Sato M. Ohkohchi Y. Ando and Y. Saito J. Phys. Chem. 1993,97,4259; S. Bandow H. Shinohara Y. Saito M. Ohkohchi and Y. Ando ihid. 1993,97 6101; T. Suzuki Y. Maruyama T. Kato K. Kikuchi and Y.Achiba J. Am. Chem. Soc. 1993 115 11 006. 23 0. Zhou R. M. Fleming D. W. Murphy M. J. Rosseinsky A. P. Ramirez R. B. van Dover and R.C. Haddon Nature 1993,362,433;M. J. Rosseinsky D. W. Murphy R. M. Fleming and 0.Zhou ibid. 1993 364. 425. 24 D. R. Buffinger R. P. Ziebarth V. A. Stenger C. Recchia and C. H. Pennington J. Am. Chem. SOC. 1993 115 9267. 25 X.-D. Xiang J.G. Hou V.H. Crespi A. Zettl and M.L. Cohen Nature 1993 361 54. 26 C.-C. Chen and C.M. Lieber Science 1993 259 655. 21 R. E. Walstedt D. W. Murphy and M. Rosseinsky Nature 1993 362 61 1; I. Hirosawa J. Mizuki K. Tanigaki T. W. Ebbesen J. S. Tsai and S. Kuroshima Solid State Commun. 1993 87 945. 28 C. Bossard S. Rigaut D. Astruc M.-H. Delville G. Felix A. Fevrier-Bouvier. J. Amiell S.Flandrois and P. Delhaes J. Chem. SOC.,Chem. Commun. 1993 333. 29 Y. Huang and D. D. M. Wayner J. Am. Chem. SOC.,1993 115 367. 40 D. A. Armitage room temperature to give bcc A,C,O. The 13C NMR spectrum of K&O shows three separate narrow lines consistent with three non-equivalent C sites. The IR spectrum of Cz; has been rep~rted.~' Laser vaporization of graphite generates C and a mixture of roughly planar polycyclic poly-yne ring isomers which on annealing in the gas-phase can be converted into fullerenes and a large monocyclic ring.,' The EPR spectrum of C& shows counter-ion-dependent anisotropy at low temperatures induced by ion pairing and two components of the high temperature spectrum the isotropic major signal and a sharp signal due to the thermal population of the low-lying excited state induced by Jahn-Teller distortion due to splitting of the 'Tlu state into 2E and 2A states.32 Electrocrystallization using [Ph,P=N=PPh,] as the counter-ion led to crystals of + the radical species [PPN]+C& while the resonance Raman spectrum ofCk; shows the pentagonal pinch mode of c60 at 1148cm-' to shift to 1462cm-' for the radical anion., The radical cation C& gives adducts with amines C: gives adducts and charge-transfer and C&+just charge-transfer to form C: and R3N.+.Both Cil and C;,+ abstract OH-from water and alcohols while multiple adducts are formed with nitriles and ethylene oxide. It is suggested that the cations of c56 and C, should be more reactive than their c60 analogues since adjacent pentagons would be present.34 Gently heating (RfC02) with c60 gives C,,(R,OH) through electron-transfer via C& in solution with addition 1,4-to a six-membered ring.35 The t-butyl-C, radical shows a barrier of 8.2 kcalmol-' to free rotation about the alkyl-C, bond and the addition of a benzyl radical is strongly facilitated by charge-transfer in the transition state., However the addition of R,Si.to c60 indicates free-rotation about the Si-C bond for R = Me or Bu'.,' Rhodium(o)-catalysed hydrogenation of C, gives the dihyride C,oH in 14% yield but this readily reverts back to c60 in the presence of oxygen. It is also formed through hydroboration and hydrolysis and shows a sharp singlet in the 'H NMR spectrum between -80 and 100"C,suggesting a static structure with reduction of the 6 6-ring bond.Deuteration to give C,,HD supports this as the ,J, coupling constant is consistent with vicinal addition.38 Calculations support spin density at the muon to be 6.6% greater than that at the 30 H. S. Chen A. R. Kortan R.C. Haddon and N. Kopylov J. Phys. Chem. 1993 97 3088; F. Rachdi J. Reichenbach L. Firlej P. Bernier M. Ribet R. Aznar G. Zimmer M. Helmle and M. Mehring Solid State Commun. 1993 87 547; W. K. Fullagar I. R. Gentle G. A. Heath J. W. White J. Chem. SOC. Chem. Commun. 1993 525. 31 J. Hunter J. Fye and M.F. Jarrold Science 1993 260 784. 32 J. Stinchcombe A. Penicaud P. Bhyrappa P. D. W. Boyd and C. A. Reed J. Am. Chem. SOC.,1993 115 5212. 33 H. Moyiyama H.Kobayashi A. Kobayashi and T. Watanabe J. Am. Chem. SOC. 1993,115 1185; M. L. McGlashen M. E. Blackwood Jr. and T.G. Spiro ibid. 1993 115 2074. 34 G. Javahery S. Petrie H. Wincel J. Wang and D. K. Bohme,J. Am. Chem. SOC. 1993,115,5716,6295,and 9701; S. Petrie G. Javahery and D. K. Bohme ibid. 1993 115 1445; S. Petrie and D. K. Bohme Nature 1993 365 426. 35 M. Yoshida Y. Morinaga M. Iyoda K. Kikuchi I. Ikemoto and Y. Achiba Tetrahedron Lett.. 1993,34 7629. 36 P.J. Krusic D.C. Roe E. Johnson J. R. Morton and K. F. Preston J.Phys. Chem. 1993,97 1736; N. M. Dimitrijevic P. V. Kamat and R. W. Fessenden ibid. 1993 97 615; M. Walbiner and H. Fischer ibid. 1993 97 4880. 37 P.N. Keiser J. R. Morton K. F. Preston and P. J. Krusic J. Chem. SOC. Perkin Trans. 2 1993 1041.38 L. Becker T. P. Evans and J. L. Bada J. Org. Chem. 1993 58 7630; C. C. Henderson and P.A. Cahill Science 1993 259 1885. C Si,Ge Sn,and Pb 41 proton in the radical C6oH and its muon isotopomer while resonance theory successfully correlates bond lengths spin densities and heats of formation of c60 C,,H. and C60H2.39 Hydrozirconation using Cp,Zr(H)Me will also reduce c60 to give (n = 1 2 3) though only to a small extent for n = 3.,O The Birch reduction of c60 has now been shown to give a range of products from C,,H18 through to C60H36 with a skewed distribution centred on C,,H, through a high-temperature redi~tribution.~' Transfer hydrogenation using 9,lO-dihydro- anthracene provides an elegent route to C6oH18 and C6oH36 while [7H]benzanthrene catalyses the conversion of C6 at 250°C into C6oH (x = 36 or 44) and C70 into C7,H3,.Deuteration occurs similarly and the structures indicate three hydrogen atoms at each pentagon leaving an isolated double bond.42 C6oH36 can also be made using hydrogen radical species and structural predictions suggest a D, or C3i (s,?) structure though a chiral T point group with four isolated aromatic benzene rings analogous to the recently synthesized C36H36 is also suggested., Adding a single-electron to C,,H is sufficient to oxidize it to c60 while methylation of C:; using Me1 gives the dimethyl derivative as a mixture of isomers (1.4 1) through dimethylation of the 6,6-bond and dimethylation 1,4 from one of the 6,6 sites.44 The X-ray structure of C60.4C6H6 showed that the position of c60 can be resolved into two orientations in the ratio 55 :45 while {m-[2-Na0,S(CH,)30]C6H3CH,}, a calix[8]arene renders c60water soluble but will not dissolve C,o.A strong CT band is observed in water at 440nm.45 C70 crystallizes with sulfur as C70.6S8 and as a hydroquinone (HQ) benzene complex C70(HQ)4.,C6H6.46 The chiral fullerene c76 can be kinetically resolved by asymmetric osmylation using OsO and a chiral alkaloid ligand and showed a specific rotation [aID of -4000" (>97e.e.) and a CD spectrum corresponding to the UV spectrum. Reduction with SnCl gives c76 as the enriched opposite enantiomer. The bis-osmylation of c60 with chiral alkaloid ligands used the mono-osmylated product to direct the second osmylation across to the opposite hemisphere.Five isomers resulted from the five possible substitution positions and their ratios depended on the Sharpless cinchona alkaloid used. With C70 substitution predominated at the 6,6-bond adjacent to the polar pentagon.47 c60 adds Ir2Cl2( 1 +COD) residues to opposite six-membered 39 M. A. Boxwell T. A. Claxton and S. F. J Cox J. Chem. Soc. Faraday Trans. 1993,89,2957; T. A. Claxton and J. Graham J. Phys. Chem. 1993 97. 4621. 40 S. Ballenweg R. Gleiter and W. Kratschmer Tetrahedron Lett. 1993 34 3737. 41 M. R. Banks M. J. Dale I. Gosney P. K. G. Hodgson R. C. K. Jennings A. C. Jones J. Lecoultre P. R. R. Langridge-Smith J. P. Maier J. H. Scrivens M. J. C. Smith C. J. Smyth A. T. Taylor P. Thorburn and A.S. Webster J. Chem.Soc. Chem. Commun. 1993 1149. O2 C. Ruchardt M. Gerst J. Ebenhoch H.-D. Beckhaus E. E. B. Campbell R. Tellgmann H. Schwarz T. Weiske and S. Pitter Angew. Chem. Int. Ed. Engl. 1993,32,584; M. Gerst H.-D. Beckhaus C. Ruchardt E. E. B. Campbell and R. Tellgmann Tetrahedron Lett. 1993 34 7729. O3 M.I. Attalla A.M. Vassallo B. M. Tattam and J.V. Hanna J. Phys. Chem. 1993 97 6329; L. E. Hall D. R. McKenzie M. 1. Attalla A. M. Vassallo R. L. Davis J. B. Dunlop and D. J. H. Cockayne ibid. 1993 97 5741; S.J. Austin R.C. Batten P.W. Fowler D. B. Redmond and R.Taylor J. Chem. Soc. Perkin Trans. 2 1993 1383. 44 T. F. Guarr M. S. Meier V. K. Vance and M. Clayton J. Am. Chem. Soc. 1993 115 9862; C. Caron R. Subramanian F. D'Souza J. Kim W. Kutner M.T. Jones and K. M.Kadish ibid. 1993 115 8505. A. L. Balch J. W. Lee B.C. Noll and h1.M. Olmstead J. Chem. Soc. Chem. Commun. 1993 56; R. M. Williams and J. W. Verhoeven Rec. Trau. Chim.des Pays-Bas 1992 111 531. 46 H. B. Burgi P. Venugopalan D. Schwarzenbach F. Diederich and C. Thilgen Helu. Chim.Acta 1993,76 2155; 0.Ermer and C. Robke J. Am. <:hem. Soc. 1993 115 10077. 47 J. M. Hawkins and A. Meyer Science 1993,260 1918; J. M. Hawkins A. Meyer and M. Nambu J. Am. Chem. Soc. 1993 115 9844; J. M. Hawkins A. Meyer and M.A. Solow ibid. 1993 115 7499. D. A. Armitage rings with 1,2,3,4-coordination to the two iridium atoms while the 19,1r Mossbauer spectra of CI(CO)(Ph3~),(C,,)Ir support q2-c60 coordination as in H(CO)(Ph,P) (C,,)Rh.48 C, reacts with (Ph,P),Pd to give q2-c6,Pd(PPh3) and similar derivatives result from C,,Pd through C-Pd cleavage using phosphines and show fluctionality which indicates rotation at the q'-b~nd.~~ The compound Cp,Fe,(CO) crystallizes with c60 as a 1 1 mixture with three molecules of benzene but Fe,(CO), Cp,MoH, Cp,TaH, and (Ph,P),Rh(CO)H all give q2-monometallic derivatives.All are stable unlike C60[Re(CO),] which forms reversibly on metallation of c60 with (CO),Re. radical^.^' Photolysing the diazomethane adduct of C, formed by [3 + 21 cycloaddition gives a 3:4 mixture of the 6,6 and 6,5 adducts C61H2. The latter results as the sole thermolysis product and shows a pair of doublets in the proton NMR spectrum due to proton inequivalence whereas the 6,6 adduct gives a ~inglet.~' The silylene (2,6- PriC,H,),Si:(Dip,Si:) formed from (Me,Si),SiDip photolytically adds to the 6,6 bond of c60 to give the silirane derivative containing a single-bonded C2Si three-membered ring.The ' and 29Si NMR spectra support this and calculations for Ph,Si suggest the 6,6 adduct to be 1~20kcalmol-' more stable than the 6,5 ad duct^.^ With Ph,C this difference is only 1.2 kcal mol- '. Thus with p-MeOC,H,(Me)CN, three products result the 6,6 adduct (1)and two involving 6,5 addition (2) and (3) which isomerize to the 6,6 derivative on overnight heating in toluene. With the oxadiazole (4) however only the 6,6-dimethyoxymethanofullerene N,N-Diethylpropynylaminesundergo photochemical [2 + 21 cycloaddition to c60 at the 6,6-bond to give the cyclobutenamine in more than 50% yield.The enamine group readily photooxidizes to give the ketoamide while SO,-catalysed hydrolysis 48 M. Rasinkangas T.T. Pakkanen T. A. Pakkanen M. Ahlgren and J. Rouvinen J. Am. Chem. Soc. 1993 115,4901; A. Vertes M. Gal F. E. Wagner F. Tuczek and P. Gutlich Inorg. Chem. 1993,32,4478; A. L. Balch J. W. Lee B.C. Noll and M. M. Olmstead ibid. 1993 32 3577. 49 V.V. Bashilov P.V. Petrovskii V.I. Sokolov S.V. Lindeman I.A. Guzey. and Y.T. Struchkov Organometallics 1993,12,991; H. Nagashima H. Yamaguchi Y. Kato Y. Saito M.-a. Haga and K. Itoh Chemistry Lett. 1993 2153. SO J.D. Crane and P. B. Hitchcock J. Chem. Soc. Dalton Trans. 1993 2537; R. E. Douthwaite M. L. H. Green A. H. H. Stephens and J. F.C. Turner J. Chem. Soc.Chem. Commun. 1993 1522; S. Zhang T. L. Brown Y. Du and J. R. Shapley J. Am. Chem. Soc. 1993 115 6705. 51 A. B. Smith 111 R. M. Strongin L. Brard G.T. Furst W. J. Romanow K. G. Owens and R. C.King J. Am. Chem. SOC. 1993 115 5829. 52 T. Akasaka W. Ando K. Kobayashi and S. Nagase J. Am. Chem. SOC.,1993 115 1605. 53 M. Prato. V. Lucchini M. Maggini E. Stimpfl G. Scorrano M. Eiermann T. Suzuki and F. Wudl J. Am. Chem. Soc. 1993. 115 8479; L. Isaacs and F. Diederich Helv. Chim. Acra 1993 76 2454. 43 C Si,Ge Sn and Pb gives the amide (5) and not the cyclobutanone and Et,NH indicating the dihydroful- lerene group to be a better leaving group than Et,NH (Equation The diphenylfulleroids with one phenyl group part of benzo-18-crown-6 reacts with cyclic conjugated enones photolytically through [2 + 21 cycloaddition to incorporate up to seven enone units.Crown-ether substituted diphenylcarbene precursors react with C60 to give benzo-crowned methanofullerenes the 6,5 adducts isomerizing to the 6,6 derivatives on heating which can be detected by electron spray MS.55 Azomethine ylides generated thermally from (Me,SiCH,)C(Bz)CH,OMe or from N-methylglycine and paraformaldehyde undergo [2 + 3) cycloaddition to c60to give the N-methylpyrrolidine derivative while another approach involves ring-opening of aziridine~.~, Disiliranes undergo photochemical [2 + 31 cycloaddition to C60 to give the 1,3-disilolane and with mesityl substituents at Si 6,6 addition gives the most stable add~ct.~' Functionalization of C, is readily achieved through [4 + 21 cycloaddition to the 6,6 bond though the reaction is often readily cycloreversed on heating.It reacts with conjugated dienes both linear and cyclic,58 anthracene in boiling naphthalene quadricyclane and tropone. 59 Benzocyclobutene homologues add similarly on pro- longed heating at 140 "C as do chemically generated o-quinodimethane derivatives formed from bis(bromomethyl)arenes.60 These do not fragment in the mass spec- trometer and using 1,2,4,5-(BrCH2),C6H2 leads to the coupling of two C60 cages.61 The addition of C60 to 5,6-dimethylene- 1,4-dimethy1-2,3-diphenylnorborn-2-en-7-one (6) involves loss of CO to give the benzocyclohexene derivative while the o-quinone 54 X. Zhang A. Romero and C. S. Foote.J. Am. Chem. Soc. 1993 115 11 024. 55 S. R. Wilson N. Kaprinidis Y. Wu and D. I. Schuster J. Am. Chem. Soc. 1993,115,8495; J. Osterodt M. Nieger P.-M. Windscheif and F. Vogtle Chem. Ber. 1993 125 2331; S. R. Wilson and Y. Wu J. Chem. Soc. Chem. Commun. 1993 784. 56 X. Zhang M. Willems and C.S. Foote Tetrahedron Lett. 1993,34,8187; M. Maggini G. Scorrano and M. Prato J. Am. Chem. Soc. 1993 115 9798. 57 T. Akasaka W. Ando K. Kobayashi and S. Nagase J. Am. Chem. Soc. 1993 115 10366. 58 B. Krautler and M. Puchberger Helv. Chim. Acta 1993,76,1626;Y.-Z. An J. L. Anderson and Y. Rubin J. Ory. Chem. 1993.58.4799;V. M. Rotello J. B. Howard T. Yadav M. M. Conn E. Vaini L. M. Giovane and A. L. Lafleur Tetrahedron Lett. 1943,34 1561; L. M. Giovane J.W. Barco T. Yadav A. L. Lafleur J. A. Marr J. B. Howard and V. M. Rotello J.Phys. Chem. 1993,97,8560;L. S. K. Pangand M. A. Wilson ibid. 1993 97 6761. 59 M. Tsuda T. Ishida T. Nogami S. Kurono and M. Ohashi J. Chem.Soc. Chem. Commun. 1993,1296; K. Komatsu Y. Murata N. Sugita K. Takeuchi and T. S. M. Wan Tetrahedron Lett. 1993 34 8473; M. Prato M. Maggini G.Scorrano and V. Lucchini J. Org. Chem. 1993,58 3613; H. Takeshita J. Liu N. Kato and A. Mori Chem. Lett. 1993 1697. 60 T.Tago T. Minowa Y. Okada and J. Nishimura Tetrahedron Lett. 1993,34,8461;F. Diederich U. Jonas V. Gramlich A. Herrmann H. Ringsdnrf and C. Thilgen Helv. Chim. Acta 1993 76 2445. 61 P. Belik A. Gugel J. Spickermann and K. Mullen Angew. Chem. Int. Ed. Engl. 1993 32 78. D.A.Armitage methide derived from o-hydroxybenzyl alcohol adds [4+ 21 to give the benzodihyd- ropyran derivatives (7).62 A range of diazocarbenes add to c60to provide functionalization on the c60surface and with the dibenzocycloheptadiene derivative (8) strong paramagnetic ring currents are observed for the first time. A diamido di-acid diphenyl fulleroid was designed specifically to inhibit an HIV enzyme as a water soluble biologically active methanofullerene. Ph(C1)C and C1 add 6,6,64 and vinyl carbenes give [l + 2) and [3 + 21 cycloadd~cts,~~ while a-halo carbanions add to both c60 and C, to give functional- ized fullerenes.66 Azides add to c60 to give azafulleroids in which the 6,5 bond is bridged,67 but amines add across the 6,6 bond,68 while the unusual temperature dependencies in the ‘H NMR spectra of polyaminated fullerenes suggest the presence of traces of water and not ‘globe-trotting’ hydrogen atoms.69 Polyoxyethylene and polyoxypropy- lene polymers with amino end-groups give fullerene derivatives with c60 and C70 which are both water and toluene soluble.70 The hemi-ketal unit appears to be present in fullerols (formed from C, and strong acids) along with tertiary hydroxy groups and Bu,NOH catalyses the reaction of c60 with aqueous NaOH to give C60(OH)24-26.71c60 and C70 have been incorporated both physically72 and 62 Y.Rubin S. Khan D.I. Freedberg and C. Yeretzian J. Am. Chem. SOC. 1993 115 344; M. Ohno T. Azuma and S. Eguchi Chem. Lett. 1993 1833. 63 L. Isaacs A. Wehrsig and F.Diederich Helu. Chim. Acta 1993,76 1231; M. Prato T. Suzuki F. Wudl V. Lucchini and M. Maggini J. Am. Chem. SOC. 1993 115 7876; R. Sijbesma G. Srdanov F. Wudl J. A. Castoro C. Wilkins,S. H. Friedman D. L. Decamp andG. L. Kenyon J.Am. Chem. SOC.,1993,115,6510. K. Komatsu A. Kagayama Y. Murata N. Sugita K. Kobayashi S. Nagase and T. S. M. Wan Chem.Lett. 1993 2163; T. Ishida T. Nogami S. Kurono and M. Ohashi Tetrahedron Lett. 1993 34 6911. 65 H. Tokuyama M. Nakamura and E. Nakamura Tetrahedron Lett. 1993,34 7429. 66 C. Bingel Chem. Ber. 1993 125 1957. 67 M. Prato Q. Chan Li F. Wudl and V. Lucchini J. Am. Chem. SOC. 1993 115 1148. 68 K. E. Geckeler and A. Hirsch J. Am. Chem. Soc. 1993,115,3850;K.-D. Kampe N. Egger and M. Vogel Angew. Chem. Int. Ed. Engl. 1993 32 1174.69 G. P. Miller J. M. Millar B. Liang,S. Uldrich and J. E. Johnston,J. Chem.SOC.,Chem. Commun. 1993,897. 70 N. Manolova I. Rashkov F. Beguin and H. van Damme J. Chem. Soc. Chem. Commun. 1993 1725. 71 L.Y. Chiang R.B. Upasani J. W. Swirczewski and S. Soled J. Am. Chem. Soc. 1993,115,5453;J. Li A. Takeuchi M. Ozawa X.Li K. Saigo and K. Kitazawa J. Chem. SOC. Chem. Commun. 1993 1784. M. W. Anderson J. Shi D. A. Leigh A. E. Moody F.A. Wade B. Hamilton and S. W. Carr J. Chem.SOC. Chem.Commun.,1993,533; Y. Wei J. Tian A. G. MacDiarmid J.G. Masters A. L. Smith and D. Li ibid. 1993 603; D. E. Bergbreiter and H. N. Gray ihid. 1993 645; H. Hungerbuhler D. M. Guldi and K.-D. Asmus J. Am. Chem. SOC. 1993 115 3386. C Si,Ge Sn and Pb 45 ~hemically,’~ into a wide range of polymers.The effect of UV light on a mixture of c60 and I gives a derivative C6,12 which contains iodine atoms trapped in a c60 lattice while c60 and I co-crystallize from toluene to give close iodine contacts with both c60 (309pm) and toluene (313 ~m).~ Electrocrystallization of C, with Ph,PI gives crystals of phosphonium stabilized C; with a deficiency of iodide while iodine monochloride doped fullerenes formed using ICl gas show superconductivity up to 60K.75Photochlorination of c60 in CCl at room temperature gives C,,CI,, while IC1 in benzene gives C,,Cl, the 13C NMR spectrum of which shows it to be isostructural with C60Br6.~~ With fluorine at 300 mm pressure fluorides result with between 35 and 44 atoms to the cage of c60 while C,,F,,, converts NaI into I, isopropanol into acetone and C,H into C,H,F.77 Hydrolysis gives a range of the mixed fluoride oxides C6,FxOy with x even and y < 18 oxygen atoms attached to the cage.78 ‘0,partly opens up the C, cage to give a diketone with a broad carbonyl stretch at about 1750cm- and MS peak at 752.It possesses a nine-membered cyclopolyalkene ring through oxidation at the 6,5 bond. C,,O results similarly.790zonolysis gives the monoxide through 0 loss and the higher fullerenes react faster than c60as the n-bond order is calculated as greater at the 6,6 bonds in the larger fullerenes than in c60.80 Calculations suggest that Ti,C; is reactive to either large dipole moments of n-bonding systems supporting a dodecahedra1 structure but theoretical studies indicate a high-spin ground state with eight unpaired electrons stability arising from the topology of the cage.The compound sc8Cl ,adopts a closed-shell structure. Ti8C and v8c1 have been isolated and are stable in air and a range of structures predicted.81 Copper carbide clusters have been detected from the reaction of copper clusters with acetylene in the gas-phase and structures predicted for [CU,,,+ ,C,J8 for n = 6 to 12.82 The structure predicted for M30C45 has D, symmetry with one C pentagon and 55 MzC3 ones. Each carbon of C forms the isolated carbon of five orthogonal M,C rings that interconnect with further M,C rings to form five M8C12 units. 73 K. Chen W. B. Caldwell and C.A. Mirkin J. Am. Chem. SOC.,1993,115 1193; J.A.Chupa S. Xu,R.F. Fischetti R. M. Strongin J. P. McCauley Jr. A. B. Smith 111 and J. K. Blasie ibid. 1993 115,4383; S. I. Khan A. M. Oliver M. N. Paddon-Row and Y. Rubin ibid. 1993,115,4919; K. L. Wooley C. J. Hawker J. M. J. Frechet F. Wudl G. Srdanov S. Shi C. Li and M. Kao ibid. 1993 115 9836. 74 Th. Zenner and H. Zabe1,J. Phys. Chem. 1993,97,8690; P. R. Birkett C. Christides P. B. Hitchcock H. W. Kroto K. Prassides R. Taylor and D. R. M. Walton J. Chem. Soc. Perkin Trans. 2 1993 1407. 75 A. Penicaud A. Perez-Benitez R. Gleason V E. Munoz P. and R. Escuder0.J. Am. Chem. Soc. 1993,115 10392; L. W. Song K. T. Fredette D. D. L. Chung and Y. H. Kao Solid State Commun. 1993 87 387. 76 F. Cataldo Gazz. Chim. Ital. 1993 123,475; P. R. Birkett A.G. Avent A. D.Darwish H. W. Kroto R. Taylor and D. R. M. Walton J. Chem. Soc. Chem. Commun. 1993 1230. 77 K. Kniaz J. E. Fischer H. Selig G. B. M. Vaughan W. J. Romanow D. M. Cox S. K. Chowdhury J. P. McCauley R. M. Strongin and A. B. Smith 111 J. Am. Chem. Soc. 1993 115 6060; A.A. Gakh A.A. Tuinman J. L. Adcock and R. N. Compton Tetrahedron Lett. 1993 34 7167. 78 R. Taylor,G. J. Langley A. K. Brisdon J. H. Holloway E.G. Hope H. W. Kroto and D. R. M. Walton,J. Chem. Soc. Chem. Commun. 1993 875. 79 C. Taliani G. Ruani R. Zamboni R. Danieli S. Rossini V. N. Denisov V. M. Burlakov F. Negri G. Orlandi and F. Zerbetto J. Chem. Soc. Chem. Commun. 1993 220. 8o D. Heymann and L. P. F. Chibante Rec. Trau. Chim. des Pays-Bas 1993 112 531 and 639. B.C. Guo K. P. Kerns and A.W. Castleman Jr. J. Am. Chem. SOC.,1993 115 7415; P. J. Hay J. Phys. Chem. 1993 97 3081; S. F. Cartier Z.Y. Chen G. J. Walder C. R. Sleppy and A. W. Castleman Jr. Science 1993 260 195; M.-M. Rohmer M. Benard C. Henriet C. Bo and J.M. Poblet J. Chem. SOC. Chem. Commun. 1993 1182. 82 I.G. Dance J. Am. Chem. SOC. 1993 115 11 052. 83 I.G. Dance Aust. J. Chem. 1993 46 727. 46 D. A. Armitage O,AsF has been used to oxidize graphite to give C,,ASF and the resulting compound characterized for n = 14 and n = 16 and AsF units were found between the graphite sheets.84 Vaporizing cyanogen with carbon gives a range of dicyanopolyynes C2,(CN) (n = 3-7 j and similar reactions with chlorine give C,CI, perchloroacenaphthylene,and decachlorocoroannulene.8 Treating polyacrylonitrile with BCI at 400°C or CH,=CHCN with BCI at 1000°C gives graphite-like semiconducting BC,N as a black powder.86 Coupling Cp*Re(NO j(Ph,PjCrCH with Cu" gives the terminally metalated butadiyne which shows bond lengths for the Re-CrC-CGC-Re chain (Re-C first) of 204 120 and 139pm whereas after oxidation with Ag+ at each Re the bond lengths become 193 125 and 133pm indicating much more cumulene character to the chain (Ret=C=C=C=C=C=Re+).87 The compound AgB(OTeF j4 reacts with CO under pressure in FCl,CCF,CI to give the Ag(C0); salt which is only stable below -15 "C.The cation is almost linear and the C-0 bonds shorter than in CO itself indicating a bond stronger than that in free CCI. Though it was not possible to determine the IR spectrum of the borate salt those of Zn(OTeF j:-and Ti(OTeF ji-both give a CO band at 2198cm-' supporting an increase in bond order on coordination to Ag.88 New carbon sulfides C,S and c6s8 result from the oxidation of C,Si -which forms a range of complexes with Mo" Wrv ReV and The 77Se spectra of C3Sez- complexes of Au"' and a range of M" ions shows more deshielding of the Se bonded to the metal for M = Ni Pd and Pt and Au"' than for Na Zn or Cd.90 Recent developments in the chemistry of silicon germanium and tin polyhedra have been briefly ~urnmarized.~' Lithium silicide LiSi results from the reaction between Li,,Si and Si under pressure.Its structure shows Si bonded to three other Si atoms with long Si-Si bonds of 250.2 pm in an open 3D network.92 Coupling Bu',SiNa with Bu\SiSiBr,SiBr,SiBu\ gives the tetrahedrane (Bu\Si),Si along with the disilane Bu\SiSiBu\ which crystallize together.The structure of the tetrahedrane shows bonds within the tetrahedron slightly shorter than the exo ones which themselves are much shorter than those in the disilane which are 268.5~m.~~ Reducing the disilane (2,6-Pr\C,H,SiC12 j2 with Mg/MgBr gives the hexasilaprismane with Si-Si bonds in the range 237.4-238.7pm and is air stable.94 Reducing Cr(CO) with KC gives K,Cr(CO) which reduces SnCI to the first octahedral Zintl anion Sni- stabilized as a complex with six Cr(CO) residues uiz. Sn,[Cr(CO),]i-. The Sn-Sn bonds are in the range 293-296 84 F. Okino and N. Bartlett J. Chem. Soc. Dalton Trans. 1993,2081;F. Okino Y.Sugiura H. Touhara and A. Simon J. Chem. Soc. Chem. Commun. 1993 562. *' T. Grosser and A. Hirsch Angew. Chem. In[. Ed. Engl. 1993 32 1340. 86 M. Kawaguchi and T. Kawashima J. Chem. Soc. Chem. Commun.. 1993 1133. 87 Y. Zhou J. W. Seyler W. Weng A.M. Arif and J. A. Gladysz J. Am. Chem. Soc. 1993 115 8509. 88 P.K. Hurlburt J. J. Rack S. F. Dec 0.P. Anderson and S.H. Strauss Inorg. Chem. 1993 32 373. " D. D. Doxsee C. P. Galloway T. B. Rauchfuss S.R. Wilson and X. Yang Inorg. Chem. 1993,32 5467; G.-e. Matsubayashi K. Douki H. Tamura M. Nakano and W. Mori ihid.. 1993 32 5990; G.-e. Matsubayashi T. Maikawa and M. Nakano J. Chem. Soc.. Dalton Trans. 1993 2995. YO G.-e. Matsubayashi and A. Yokozawa Inorganica Chim. Acta 1993 208 95. 91 M. Weidenbruch Angew.Chem. Int. Ed. Engl. 1993 32. 545. 92 J. Evers G. Oehlinger and G. Sevtl Angew. Chrm.. Int. Ed. Engl. 1993 32 1442. 93 N. Wiberg C.M. M. Finger and K. Polborn Angew. Chem. Int. Ed. Engl. 1993 32 1054. 94 A. Sekiguchi T. Yatabe C. Kabuto and H. Sakurai J. Am. Chem. Soc. 1993 115 5853. y5 B. Schiemenz and G. Huttner Angew. Chrm. Int. Ed. Engl.. 1993 32 297. C Si,Ge Sn and Pb 47 Mes,Si adds to tetramethylbutatriene to give the first bis(alky1idene)silirane (sila[3]radialene) and the first indenylgermylenes result from 1 ,3-(Me,Si),C9H,Li and GeCl,.di~xane.~~ The compound [2,4,6-(CF,),C,H,],Sn reacts with oxygen to give the cyclotristannoxane while the plumbylene Is,Pb results from Is*Li and [(Me,Si),N],Pb and can be trapped by MeI Ph,S, and Ph,Se,.97 Attempts to prepare three-coordinate silicon cations without solvent or anion interaction have proved to be difficult.In benzene R,Si-H and Ph,C+B(C,F,) give the silyl cation and 29Si NMR spectra support reduced coordination from the anion. The crystal structure for the ethyl derivative confirmed this showing no interaction with the anion and only a distant one from the toluene the solvent of crystallization. The bromocarborane derivative PrlSi(Br,CB,H,) shows only a weak Si --Br interaction of 246 pm and like the borate a 29Si shift of about 100 ppm from TMS.98 The first stable 1-silaallene results from the coupling of a highly-hindered alkyne with Mes*AdSiF and shows Si-C and C-C bond lengths of 170.4 and 132.4pm re~pectively.~~ The fluorenylidene derived germene adds two moles of Bu'CEP to give a germadiphosphatricyclooctene while analogous stannenes add a range of protic reagents.loo The disilene complex Cp,W(y'-Me,Si=SiMe,) reacts with Me,N+-O- to give the four-membered metallodisiloxane ring while chalcogens also give the symmetrical insertion product.With phosphine sulfides however the W-Si bond is inserted to give the unsymmetrical four-membered ring and is slightly favoured for small phosphine sulfides but not at all for hindered ones."' The highly-hindered disilene Tb(Mes)Si=Si(Mes)Tb (Tb = 2,4,6-[(Me,Si),CH] ,C,H2) thermally dissoci- ates into the less-hindered silylene while reaction with oxygen gives the cyclo- disiloxane.' O2 Pol ysilacycloalkynes result from the dichloropolysilane and an acetylene di-Grignard reagent.Hexasilacyclooctyne photolytically ring-contracts with loss of dimethylsilylene to give the cycloheptyne and cyclohexyne this latter readily adding silylene to give the bicyclic derivative (9) and diphenylcarbene to give the cumulene (lO).lo3 Eight- seven- and six-membered polysilacycloallenes result similarly using Me,SiCH,CECSiMe, BuLi and dichloropolysilanes the smaller rings showing the greater divergence from linearity at the C unit. The seven-membered ring has an angle of 174.1' at the middle carbon atom but this is 166.4' for the six-membered ring (1 1). The C-phenyl substituted derivatives have angles of 174 and 161" re~pectively."~ Coupling allene to Cl(SiMe,),Cl or condensing with hexachloropropene using Mg 96 T.Yamarnoto Y. Kabe and W. Ando Organometallics 1993,12,1996;A. H. Cowley M. A. Mardones S. Avendano E. Roman J. M. Manriquez and C.J. Carrano Polyhedron 1993 12 125. 97 H. Grutzmacher and H. Pritzkow Chcm. Ber. 1993 125,2409; K. Shibata N. Tokitoh and R. Okazaki Tetrahedron Lett. 1993 34 1495. 98 J. B. Larnbert and S.Zhang J. Chem.Soc.,Chem. Commun. 1993,383;J. B. Lambert S. Zhang C. L. Stern and J.C. Huffrnan Science 1993 260 1917; Z. Xie D.J. Liston T. Jelinek V. Mitro R. Bau and C.A. Reed J. Chem. SOC.,Chem. Commun. 1993 384. 99 G. E. Miracle J. L. Ball D. R. Powell. and R. West J. Am. Chem. Soc. 1993 115 11 598. 100 M. Lazraq J. Escudie C. Couret U. Hergstrasser and M. Regitz J. Chem. Soc. Chem. Commun. 1993 569;G.Anselme J.-P.Declercq A. Dubourg. H. Ranaivonjatovo J. Escudie and C. Couret J. Organomet. Chem. 1993 458 49. 101 P. Hong N. H. Damrauer P. J. Carroll and D. H. Berry Organometallics 1993 12 3698. lo' N. Tokitoh H. Suzuki R. Okazaki and K. Ogawa J. Am. Chem. Soc. 1993 115 10428. F. Hojo S. Sekigawa N. Nakayama T. Shimizu and W. Ando Organornetallics 1993 12 803; S. Sekigawa T. Shimizu and W. Ando Tetrahedron 1993 49 6359. Y. Pang. S. A. Petrich V. G. Young Jr. M. S. Gordon and T.J. Barton J. Am. Chem. Soc. 1993 115 2534; T. Shimizu F. Hojo and W. Ando ihid. 1993 115 3111. D. A. Armitage MezSi,/-\ ,SiMep Me3Si *CSCSiMe3 Si-Si C Me2 Me2 Ph2 (9) Me2 Me2 Me2Si-SiMe2 st-si I\ \ / \Ye2 Me2Si I1 ,SiMe2 Me2Si C /c=c=c\ C Me2Si C \ Fe2 I1 Me2Si' 'SiMe2 Si-Si \/ Me2 Me2 Si-Si Me2 Me2 gives the octasila[4.4]allene (12) along with the exocyclic allene (13).Spectral features indicate little strain in the endo isomer but at 520 "C it is cleanly converted into the em isomer.lo5 An extensive range of hindered tris(trimethylsily1)silyl derivatives have been synthesized the disilane (Me,Si),SiSi(SiMe,) having a long central Si-Si bond of 240 pm. It results from (Me,Si),SiLi(thf), using PbCl as oxidizing agent while (Me,Si),GeLi and PbCl give the digermane and the distannane results from coupling Me,SiLi with SnCl,. The diplumbane has not been made. Coupling (Me,Si),SiLi(thf) with Ph,PbCl gives the diplumbane { [(Me,Si),Si]Ph,Pb) which is thermochromic and possesses a Pb-Si bond of 264.8 pm and Pb-Pb bond of 291.1 pm.lo6 Treating (Bu'CH,),Sn with potassium in THF gives the stannyl-potassium derivative.In toluene this crystallizes to show K in a distorted tetrahedral environment with three molecules of toluene q6 to K a K-Sn bond of length 354.8pm and a -P coupling constant of 289 Hz.lo7 The Si-B single bond in Cy,P BH,SiMe is 200.7 pm while Cp,Ta(PMe,)(SiBu\H) activates L.BH to give the q2-BH,(SiBu\)H complex. This with PMe, gives the q'-complex and the q2-and ql-complexes have Si-B bonds of 202 and 203 pm respectively. Excess Me,P displaces the silylborohydr- ide ligand as its phosphine complex (Equation 2).'08 The metal-silylene complex Bu\Si=Cr(CO) .NaOTf.2THF shows multiple bond character at the Cr=Si bond (247.5pm) and triflate coordination at Si with a Si-0 bond length of 185.7pm.Both pyridine and CO eliminate the silylene from the S.A. Petrich Y. Pang V.G. Young Jr. and T.J. Barton J. Am. Chem. Soc. 1993 115 1591. H. Bock J. Meuret and K. Ruppert J. Organomet. Chem. 1993,445,19 and Angew. Chem.,Int. Ed. Engl. 1993,32 414; S. P. Mallela and R. A. Geanangel Inorg. Chem. 1993 32 5623 and 602. lo' P. B. Hitchcock M. F. Lappert G.A. Lawless and B. Royo J. Chem. SOC.,Chem. Commun. 1993 554. A. Blumenthal P. Bissinger and H. Schmidbaur J. Organomet. Chem. 1993 462 107; Q. Jiang P. J. Carroll and D. H. Berry Organometallics 1993 12 177. C Si Ge Sn and Pb 'I' H-BH2Si( H)But2 Cp2Ta, ,H ,B ,SiBut2-C&Ta / H H Me3P \ &CppTa(PMe3)H + Me3P-cBH2Si(H)But2 (2) p*3 complex which trimerizes to (Bu',Si),.'Og Aryl substituted silylenes can also be stabilized on the metal through o-substituted donor groups.Thus 2-(Ph,PCH,C,H,),Si=Cr(CO) shows a dynamic 'flip-flop' coordination of each phosphorus to the silicon in solution and in the solid state and a Cr-Si bond length of 241.4pm and P -+ Si coordination (238.0pm) from only one phosphino group. Photolysis causes a 1,2-shift of the phosphine to Cr with CO displacement to give the trans substituted tricarbonyl (Equation 3).'' Structure determinations of Ph,SiNH, Mes,Si(NH,), and 2,4,6-Ph3H,Si(NH,) show Si-N bonds of similar length in each ranging from 170.8 to 171.7 pm. All these compounds show pyramindal character at nitrogen which tends to indicate a lack of n-bonding in these examples.' '' The spectral properties of the twisted Si=N bonds observed in the bridgehead silanimines formed from the photolysis of l-azido-l- silabicyclo[2.2.llheptane and [2.2.2]octane suggest that n-bonding plays a crucial role in determining the properties of silanimines. With the bicycloheptane the two possible silanimines (14) and (1 5) form in 1:3 ratio [presumed from the ratio of their adducts with MeSi(OMe),] (Equation 4). '' Photolysing PhSi(N,) is thought to give the isosilacyanide PhN=Si uia the silonitrile PhSi-N since although PhSiEN cannot be detected Bu'OH gives PhSi(NH,)(OBu') as well as PhNHSiH(OBu'),.' Coupling (BrH,SiCH,) with hydrazine in the presence of triethylamine gives the 109 H.Handwerker M. Paul J. Riede and C. Zybill J. Organomet. Chem. 1993,459 151. 110 H. Handwerker M. Paul J. Blumel and C. Zybill Angew. Chem. Int. Ed. Engl. 1993 32 1313. Ill K. Ruhlandt-Senge R.A. Bartlett M. M. Olmstead and P.P. Power Angew. Chem. Int. Ed. Engl. 1993 32 425. 112 J.G.Radziszewski P. Kaszynski D. Littmann V. Balaji B. A. Hess Jr. and J. Michl J. Am. Chem. SOC. 1993 115 8401. 113 J.G. Radziszewski D. Littmann V. Balaji L. Fabry G. Gross and J. Michl Organometallics 1993 12. 4816. D.A. Armitage diazatetrasila[4.4.0]bicyclodecane (16); the use of (BrH,SiCH,),CH yields the biscyclohexyl derivative (17). While the N-NSi unit is planar they are not orthogonal in (16) owing to conformational constraints. In (17) the absence of these constraints allows the N-NSi units to be at 9Oo.'l4 Sodium tri(pyrazo1-y1)-germanateand stannate salts result from the reaction of pzNa with GeCl,.dioxane and SnC1 in THF in the ratio 3 1.The germanium anion (pz),Ge-acts as a tridentate ligand to Nat giving a monomeric derivative while the tin anion bridges two sodium ions giving a dimeric species with one non-bridging pyrazolyl group on each tin atom.' ' Azagermatranes methylated at nitrogen react with N(CH,CH,NH,) to give azagermatrane protonated at nitrogen. This reaction is not reversible but both azagermatranes react with the trio1 N(CH,CH,OH) to give the germatrane.' ' Azastannatranes result similarly and show axial Sn-N bond lengths of 236.8pm in Me,NSn(NMeCH,CH,),N some 31 pm longer than the equatorial lengths.With the phenyl derivative PhSn(HNCH,CH,),N two different structures have been observed within the lattice with axial bonds being 238 and 245 pm.' l7 Reacting the stannylene [(Me,Si),N],Sn with 2,6-Pr\C6H,N (DippN,) gives the stannaimine below -30 "C the structure showing planarity at nitrogen and Sn-N bond lengths of 192.1 201.5 and 203.0pm. Above -3O"C but below O"C C-H insertion at the isopropyl group occurs to give the stannadihydroindole (1 8) while at -50 "Cexcess azide gives the 1,3-adduct (19) if 2,6-Et2C,H,N is used."' R pN [(Me3Si)2N]2Sn I I NRN R (19) R = 2,6-Et&H3 Dimethyltin dichloride completely substitutes (Me,Sn),N to give the first function- alized tristannylamine. The structure shows a planar NSn skeleton stabilized by intramolecular chloride bridges.The Sn-N bonds are between 197 and 201 pm while the Sn-Cl distances vary from 269.6 to 282.4 pm.' l9 The first imino-lead complex N. W. Mitzel P. Bissinger J. Riede K.-H. Dreihaupl and H. Schmidbaur Organometallics 1993,12,413. 'I5 A. Steiner and D. Stalke J. Chem. SOC.,Chem. Commun.,1993 1702. Y. Wan and J.G. Verkade Znorg. Chem. 1993 32 79. W. Plass and J. G. Verkade Znorg. Chem. 1993 32 5145 and 5153. G. Ossig A. Meller S. Freitag and R. Herbst-Irmer J. Chem. SOC.,Chem. Commun. 1993 497. C. Kober J. Kroner and W. Storch Angew. Chem. Znt. Ed. Engl. 1993 32 1608. C Si Ge Sn and Pb 51 Pb[N=C(Bu')Ph],Li.THF results from the reaction of Cp,Pb with LiN=C(Bu')Ph and possesses a distorted trigonal bipyramidal PbN,Li core with Pb-N bonds of 233 pm while the phenyl groups encapsulate lead with Pb *.* C bond lengths to the ortho carbon of 321-331 pm though no 13C-207Pb coupling is observed.12' Coupling the 1,3-diphospha-2-silaallyl anion [ArPSi(Bu')PAr] -[Li(E20),] + with Ph,PCl gives the 1,3,4-triphospha-2-silabut-l-ene, yellow crystals of which show Si-P bonds of 209.4 and 225.4pm supporting double bond character in the first Si-P bond.'21 The arsasilene Is,Si=AsSiPr\ (Is = 2,4,6-Pr\C6H2) adds to Ph,CO(l 1) to give arsa-alkenes and to isonitriles (1 :2) to give arsaalkene substituted l-aza-3- silacyclobutanes.'22 The compound Bu'GeF condenses with PriSiAsHLi then BuLi to form the arsenide { Bu'Ge[As(SiPr:)Li],) which contains a Ge,As,Li cage with Ge-As bonds of about 245 pm and Si-As bonds of 233 pm.', Na,SnAs has been formed from the molten elements and shown to contain adamantane-like Sn,As, units interconnected by terminal As atoms in a 3D framew~rk.'~~ Rice-hull heated at 723 K gives ash containing 92% SiO,.With 5% NaOH catalyst this ash reacts with dimethyl carbonate at 625 K to give a 95% yield of (MeO),Si in a few Refluxing BaO silica and glycol followed by removal of the water dissolves the silica in a few hours to give high yields of the hexaalkoxysilicate Ba[Si(OCH,CH,O),] which contains octahedral silicate anions that coordinate to Ba2+ through nine 0 + Ba2+ interactions of 320pm or less.', Penta-and hexa-coordinate silicon compounds have been reviewed.' 27 The siliconate [Si(O,C6H,-1,2),{C,H,(CH,NMe,),-2,6}] -shows only one amino group coordinating to Si and added MeOH strongly hydrogen bonds to the non-coordinated amino group and a catecholate oxygen atom.This interaction prevents exchange between the two amino groups.12* The hydrogen bonding in (HOSiMe,),O shows zig-zag double chains with consecutive hydrogen bonds alternating from within chain to between chain (20). There is no hydrogen bonding between these double chains. The hexaphenyl substituted trisiloxane- 1,5-diol possesses a hydrogen bonded eight-membered ring which dimerizes to give an eight-membered H,O ring (21).'29 In attempting to prevent solvent loss from crystals of K+[InH(CH,CMe,),] by using high-vacuum silicone grease for protection needle shaped single crystals of [K+],[K(Me,SiO),f][InH(CH,CMe,),] were formed in which the cyclo-heptasiloxane is planar with almost D, symmetry and crowns K+ with K *.0 bond lengths of between 286 and 299 pr11.'~' The disiloxane diolate anion Si,Ph,O(OLi) is A.J. Edwards M. A. Paver P. R. Raithby C. A. Russell and D.S. Wright,J. Chem.SOC.,Chem. Cornmun. 1993 1086. H.R.G. Bender E. Niecke and M. Nieger J. Am. Chem. SOC. 1993 115 3314. M. Driess H. Pritzkow and M. Sander Angew. Chem. Int. Ed. Engl. 1993 32 283. L. Zsolnai G. Huttner and M. Driess Angew. Chem. Int. Ed. Engl. 1993 32 1439. lZ4 M. Asbrand and B. Eisenmann Z. Naturforsch. Teil B 1993 48 452. lZ5 M. Akiyama E. Suzuki and Y. Ono Inorg. Chim. Acta 1993 207 259. M.L. Hoppe R. M. Laine J. Kampf M.S. Gordon and L. W. Burggraf Angew. Chem. Int. Ed. Engl. 1993 32 287. 127 C. Chuit R. J. P. Curriu C. Reye and J.C. Young Chem. Rev. 1993 93 1371. Iz8 F. Carre C. Chuit R. J. P. Corriu A. Mehdi and C. Reye J. Organornet. Chem. 1993 446,C6. 129 P. D. Lickiss A. D. Redhouse R. J. Thompson W. A. Stanczyk and K. Rozga,J. Organornet. Chem. 1993 453 13; H. Behbehani B. J. Brisdon M. F. Mahon K. C. Molloy and M. Mazhar ibid. 1993 463 41. I3O M. R. Churchill C. H. Lake S.-H. L. Chao and O.T. Beachley Jr. J. Chem. SOC.,Chem. Commun. 1993 1577. D.A. Armitage dimeric in dioxane and forms a range ofcomplexes with Ba2 + ,Zr4+ ,Hf4' ,Cr3+ ,and Co3+. The barium derivative contains an unusual Ba,O core in which Ba2+ is encapsulated in a Ba,(Si20,) cage.',' Reaction of the tetraol (HOCH,),CHCH(CH,OH) [L(OH),] with RGeCl (R = Ph Me) gives the neutral L(OH)O,GeR.Deprotonation of this product to give the square pyramidal germanium(1v) anion requires the strong base P(MeNCH,CH,),N(P*) but efforts to obtain single crystals of [P*H] +[LO,GeR] -have so far failed. 32 The first diorganotindihydroxide [(CpFeC,H,-2-CH2NMe2),Sn(OH),I .2CHCl, to be reported shows dimerization through hydroxy bridges rather than nitrogen c~ordination.'~~ Organothio groups stabilize silylene complexes of platinum with [(Cyp,P),HPt=Si(SEt),]+ showing both a short Pt-Si bond and short Si-S bonds of 207.4 and 209.2pm some lOpm shorter than single bonds. The complex [Cp*(Me,P),Ru=Si(STol)Os(CO),] also shows short M-Si and short Si-S bond + lengths.' 34 The first diarylgermanethione TbTipGe=S (22) results from the desulfurization using PH,P of the tetrathiametallolane.The structure of the orange-yellow crystals m.p. 163-165 "C exhibit a Ge-S bond length of 204.9pm much shorter than the single bond value of 221 pm. It also results from the germylene and styrene episulfide and gives cyclic adducts with dienes PhNCS and mesitonitrile N-oxide. The hydroxy- mercaptogermane results upon reaction with water (Equation 5). 35 131 M. Motevalli D. Shah and A.C. Sullivan J. Chem. SOC.,Dalton Trans. 1993 2849; M. Motevalli M. Sanganee P. D. Savage S. Shah and A.C. Sullivan J. Chem. SOC. Chem. Commun. 1993 1132; I. Abrahams M. Motevalli D. Shah A.C.Sullivan and P. Thornton ibid. 1993 1514; J.A. Darr S. R. Drake D. J. Williams and A. M. Z. Slawin ibid. 1993 866. 132 M. Ye and J. G. Verkade Inorg. Chem. 1993 32 2796. 133 K. Jurkschat C. Kruger and J. Meunier-Piret Main Group Metal Chem. 1992 15 61. 134 S. D. Grumbine T. D. Tilley F. P. Arnold and A. L. Rheingold J. Am. Chem. SOC.,1993,115,7844;S. D. Grumbine and T. D. Tilley ibid. 1993 115 358. 135 N. Tokitoh T. Matsumoto K. Manmaru and R. Okazaki J. Am. Chem. SOC. 1993 115 8855. C Si,Ge Sn and Pb 53 The first thiastannirane results from addition of the stannylene [(Me,Si),CH],Sn to di-t-butylthioketene and has a very acute C-Sn-S angle of 45.7" and a short C-S bond. The stannylene couples less-hindered thioketones to give thiastannolanes.' 36 The first 1,2-thiastannete and 1,2-~elenastannete resulted from sterically crowded trichalcogenastannolates through [2 + 2lcycloaddition of stannanethione or selone to MeOCOC=CCO,Me.The structures of these stannetes show the C=C bonds are 133 pm in each the Sn-S and Sn-Se bonds are 265.1 and 274.6 pm respectively so that the Sn-C ring bond in the latter is 230pm some 13pm longer than that in the thiastannete. ' With Na,S in crypt [Cp*(CO),Mn=],Sn furnishes the Na(THF),Sn,S anion as a cube-like structure with each Sn atom bonding to a Mn residue.',* A range of alkali metal tin polysulfides exhibit SnS tetrahedra and SnS octahedra cross-connected through Si-units to give [SnS,]i"- chains. With SnS ,octahedral tin is present with two Si-and one Si-chelating ligands while [SnCl,(S,),]2- shows trans chlorine atoms.13' Adding SnCl to a borohydride reduced solution of Li,Te/Te gives the anion Sn,Te;-comprising edge-bridged tetrahedra with shorter terminal (268.6 pm) Sn-Te bonds than bridged ones (28S282 pm).140 The di-lead trichalcogenide anions Pb,S,Se; I and Pb,S,Tei I (n ==0-3) and Pb,SSeTe2 -can be obtained from alloys by reaction with potassium. The structures of Sn,X;- (X = Se Te) show a D, trigonal bipyramid with Sn-Se distances of 265pm and Sn-Te bonds of 288.7~m.I~' Te Te [(Me$3)2Nl2Sn +2(Me&i)&TeH -. %3P -SnlTeSi(SiMe3)& (6) (23) Si omitted for clarity (Me,Si),SiTeLi crystallizes from cyclopentane as a solvated hexameric cage with a centrosymmetric hexagonal prism-like structure involving a slight boat structure at the hexagonal face and Li and Te atoms at the vertices.142 The parent tellurol reacts with [(Me,Si),N],M (M = Sn Pb) to give the dimeric [(Me,Si),SiTe],M the structure of the tin derivative confirming the butterfly-like dimeric structure (23) and terminal bonds (280 pm) are shorter than the bridge bonds (295 pm) (Equation 6). Me,P cleaves the bridge to give a 1 1 complex while pyrolysis at 250 "C provides a low temperature route to cubic SnTe PbTe and PbSe (using the selenol). Lanthanide tellurides can be prepared similarly by pyrolysing [(Me,Si),SiTe],M (M = La Ce) at 600"C.143 136 T. Ohtaki Y. Kabe and W. Ando Organometallics 1993 12 4. 13' N. Tokitoh Y. Matsuhashi and R. Okazaki J. Chem. SOC.,Chem.Commun. 1993 407. 13' B. Schiernenz F. Ettel G. Huttner and L. Zsolnai J. Organomet. Chem. 1993 458 159. 139 J.-H. Liao C. Varotsis and M. G. Kanatzidis lnorg. Chern. 1993,32,2453;W. Bubenheirn and U. Muller 2. Anorg. Allg. Chem. 1993 619 779. M.A. Ansari J. C. Bollinger and J. A. Ibers lnorg. Chem. 1993 32 231. 14' M. Bjorgvinsson H. P.A. Mercier K. M. Mitchell G.J. Schrobilgen and G. Strohe Inorg. Chem. 1993 32 6046. 14' G. Becker K. W. Klinkharnmer and W. Massa 2. Anorg. Allg. Chem. 1993 619 628. 143 A. L. Seligson and J. Arnold J. Am. Chcm.SOC.,1993,115,8214; D. R. Cary and J. Arnold ibid.,1993,115 2520. 14' D.A. Armitage rn-and p-Bis[(difluoro)phenylsilyl)benzenes readily accept fluoride at each silicon to give pentacoordinate dianions with axial bonds of about 6pm longer than the equatorial ones.Equimolar quantities of the disilarene and dianion quickly equilibrate to the mixed derivative as one site is a fluoride donor and the other a fluoride acceptor. As determined by 13CNMR spectroscopy ap’ for difluoro(pheny1)silyl was found to be significantly reduced on flu0ridati0n.I~~ Reacting Me,PbCI with SbCl and 18- crown-6 gives the complexes [Me,Pb(l8-~rown-6)]~+[SbCl~], and CPbCl(18-crown-6)] [SbCl; J which shows Pb in a hexagonal planar array of six oxygen atoms + with C1 axial. Treatment of PbCl with 18-crown-6 gives [Pb( 18-crown-6)(MeCN),] 2+ in which the ether crowns lead but with 15-crown-5 the sandwich complex [Pb(15-crown-5)J2+ is f0~med.l~~ 144 M. Kira T. Hoshi C.Kabuto and H. Sakurai Chem. Lett. 1993 1859. 145 H. von Amim K. Dehnicke K. Maczek and D. Fenske 2. Anorg. Allg. Chem. 1993 619 1704.

ISSN:0260-1818    

DOI:10.1039/IC9939000037

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

5 N P As Sb and Bi By D.A. ARMITAGE Department of Chemistry King's College London Strand London WC2R ZLS UK This review follows the pattern of that last year and covers the 1993 literature. The heterogeneously-catalysed synthesis of ammonia from nitrogen and water reported some years ago has attracted debate and the stability of cyclopentazoles and other poly-azo rings has been highlighted.' General reviews have covered phospha-alkynes,2 the coordination and organometallic chemistry of pho~phazenes,~ monocyclic and polycyclic phosphanes? antimony homocycles and heterocycle^,^ and the structure colour and chemistry of penta-aryl bismuth compounds.6 Organoantimony and bismuth chemistry has been surveyed for 1990.7 1 Halogen Derivatives P,Cl results from reducing PCI with Cu it is inflammable in air and undergoes 1,2-addition to cyclohexene and cy~lohexa-1,4-diene.~ MCl (M = As or Sb) and tetramethylcyclam L yields upon hydrolysis the bridged chloroxo anions [H,L]- [M,0,C1,0].9 The I2'Sb Mossbauer spectra ofcrown ether adducts of SbCl show the Sb lone pair has variable stereochemical activity according to the nature of the crown used." SbI gives a distorted octahedral structure with 1,4,7-trithiacyclonoane.' The anions Sb&; (1)and Sb,I:; (2) result from the hydrolysis of SbI and contain iodine bridged clusters in which each Sb is octahedrally surrounded by iodide ions.In (l),two rows of four Sb"' ions are connected by bi- and tri-dentate iodide ions while (2)has a square pyramid of Sb"' ions connected by one pentadentate iodide ion four bidentate in the base and four connecting the base with apex.The neutralizing cations are [H(HMPA),]+ .I2 The anion [SbI,(Me,PCH,CH,PMe,)] -shows distortions which were interpreted in terms of an arrested double S,2 transition state for the substitution 1 V. Augugliaro J. Soria L. Palmisano M. Schiavello A. Sclafani J. A. Davies and J. G. Edwards Angew. Chem. lnt. Ed. Engl. 1993 32 550; R Janoschek ibid. 1993 32 230. 2 J. F. Nixon Chem. Ind. (London) 1993 404. 3 V. Chandrasekhar and K. R. J. Thomas Appl. Organomet. Chem. 1993 7. 1. 4 M. Baudler and K. Glinka Chem. Rev 1993,93 1623. 5 H. J. Breunig Main Group Metal Chem. 1993 16 143. 6 K. Seppelt in 'Advances in Organometallic Chemistry' ed. F. G. A.Stone and R. West J. Wiley and Sons 1992 34,207. 7 L. D. Freedman and G. 0.Doak J. Organomet. Chem. 1993 442 1 and 61. 8 M. Driess and G. Haiber Z. Anorg. Allg. Chem. 1993 619 215. 9 G. R. Willey A. Asab M.T. Lakin and N. W. Alcock J. Chem. Soc. Dalton Trans. 1993 365. LO M. Takahashi T. Kitazawa and M. Takeda J. Chem. Soc. Chem. Commun. 1993 1779. 11 S. Pohl D. Haase and M. Peters 2. Anorg. Allg. Chem. 1993 619 727. 12 C. J. Carmalt N. C. Norman and L. J. Farrugia Polyhedron 1993 12 2081. 55 56 D. A. Armitage of two iodide anions by dmpe.' BiI and (Me,N),PO react to give a centrosymmetric dimeric 1 1 complex in which Bi,I units weakly interact to give a polymer containing octahedrally coordinated Bi with HMPA ligands being equatorial and trans to bridging iodine atoms.With excess HMPA the ionic complexes [BiI,(HMPA),] '[I,] -(n = 3 or 5) re~u1t.I~ With Me,S the ionic complex [Me3S]~[Bi,I,(SMe,)2]2- is formed in which the anion has an edge-shared bioctahedral structure with the weakly bound sulfide ligands axial and trans. Benzene gives a 1 :1 complex with BiCl on cooling to -15 "C and the structure indicates a centrosymmetric dimer with the benzene molecules weakly n-bonding to bismuth There are additional weak interactions between the non-bridging chlorine atoms and bismuth in adjacent dimer units. Xylene complexes show similar struc- tures.16 The THF complex of PhBiCl is chloride bridged and square-pyramidally coordinated with a weak n-interaction of the phenyl group at the sixth coordination site of Bi.The anion [Bi,Ph2Br,l2 -has a centrosymmetric base-bridged structure with a planar Bi,Br unit while [BiPh,I,] -exhibits a dimeric structure having bridged trigonal bipyramids with axial phenyl groups.' 2 Chalcogen Derivatives Thioxophosphanes can be stabilized as monomers at room temperature if ylide-substituted and can be oxidized to the dithioxophosphorane (Equation I) while bulky aryl substituents stabilize selenium analogues.' S Na2S c Ph,P=C(R)P=S 8Ph,P=C(Et)PS (1) PhSP=C(R)PC12 R = El a-P,S312 with Bu",nH gives &-P,S,H which is unstable in solution. l9 The phase diagrams for the system M,X (M = P As; X = S Se) show all possible mixed PAS sulfides and P sulfide/selenides. Compounds of the type M,X3 were also detected.,' Two isomers of P-P,S,SeI and P-P,SSe,I have been identified and result from the reaction of P,S,- Sen with I,." P,S and [CpCr(CO),] give a tetranuclear complex Cp,Cr,(CO),P,S in which two of the Cr residues bond to chelating PS species and bond Cr atoms across two P atoms of the isomerized P,S3 residue., Ph,P-S- functions as a bridging ligand to Pd l3 W.Clegg M. R. J. Elsegood V. Graham N. C. Norman and N. L. Pickett J. Chem. SOC.,Dalton Trans. 1993 997. l4 W. Clegg L. J. Farrugia A. McCamley N. C. Norman A. G. Orpen N. L. Pickett and S. E. Stratford J. Chem. SOC.,Dalton Trans. 1993 2579. W. Clegg N. C. Norman and N. L. Pickett Polyhedron 1993 12 1251. l6 W. Frank J. Schneider and S. Muller-Becker J. Chem. SOC.,Chem. Commun. 1993 799; Z.Anorg. Allg. Chem. 1993 619 1073. 17 W. Clegg R. J. Errington G. A. Fisher R. J. Flynn and N. C. Norman J. Chem. SOC.,Dalton Trans. 1993 637. G. Jochern H. Noth and A. Schrnidpeter Angew. Chem. Int. Ed. Engl. 1993.32 1089; M. Yoshifuji M. Hirano and K. Toyota Tetrahedron Lett. 1993 34 1043. l9 B. W. Tattershall and N. L. Kendall J. Chem. SOC.,Dalton Trans. 1993 3163. 2o R. Blachnik P. Lonnecke and J. Nuss Z. Naturforsch. Teil B 1993 48 1175. P. Lonnecke and R. Blachnik Z. Anorg. Allg. Chem. 1993 619 1257. 22 L.Y. Goh W. Chen and R.C. S. Wong Angew. Chem. Int. Ed. Engl. 1993 32 1728. N P,As Sb and Bi and Pt and as a chelating ligand to Pd,23 while (Bu\PCH,),PMe obtained from Me,PCH,Li and BuiPCl coordinates to the Mo(CO) residue and adds sulfur.24 [q5-C,Me,EtCo(CO)] gives a range of di- and tri-metallic derivatives with As,S at 80 0C,25 while the diarsenidene complexes [(q5-MeC,H,(CO),Mn),As],X (X = S Se) result from the chloride using Na,X.26 Ph,SbCl and (Ph,Sb),X (X = 0,S) complex with Cr Mo and W carbonyl residues,27 while Me,SbXMe(X = S Se) has Sb-X bonds of 242 and 256pm respectively in the vapour phase.28 The anion Sb,S:; has each Sb atom present in a chair SbS ring and both are present in a Sb,S ring with Sb atoms at positions 1 and 3.29 The Zintl anions Sb,Te:- and Sb,Te;-result electrochemically from Sb,Te3 the former showing a Sb four-membered ring and the latter two fused Sb rings and two Sb3Te rings.30 Condensing (Bu'PCl) with Na,Te gives the telluradiphosphirane and this along with other P-Te heterocycles (Bu'P),Te (n= 3 or 4; rn = 1 and 2) result from the reaction of chlorophosphane with (Me,Si),Te or Bu'P(SiMe,) and Te.3 3 Oxygen Derivatives The tetra-t-butylbicyclo[3.1.O]hexaphosphane is oxidized3 at positions 2 and 4using cumene hydroperoxide during the preparation of P,O,S and P,06S3.Coupling [Cl,(O)P],CF with P,SlO gives P,O,(CF,),S with terminal P=S bonds and CF groups bridging P atoms along a two-fold axis.33 (EtAsO) occurs in solution as a mixture of cyclic trimer and tetramer but reaction with M(CO) provides a template for ring expansion to give [M(CO),],(E~ASO),.~~ 4 Unsaturated Organophosphorus Compounds (Et,P),Pt reacts with mes*P=CCl to give an intermediate cyclobutenyl-Pt complex with a non-aromatic ring (3) that eliminates the phosphyne on warming (Equation 2).35 - -p (Et3P) Pt + rnes*P =CC12 Me s'P 'b-Pt(PEt&CI -+ m es%,P CI' Pt(PEtJ,CI (2) (3) 23 J.Fornies F. Martinez R. Navarro E. P. Urriolebaitia and A. J. Welch J.Chem.Soc. Dalton Trans.,1993 2147. 24 J. Krill I. V. Shevchenko A. Fisher P.G. Jones and R. Schmutzler Chem. Ber. 1993 126 2379. 2s H. Brunner B. Nuber L. Poll and J. Wachter Angew. Chem. Int. Ed. Engl. 1993 32 1627. 26 Ch. Emmerich G. Huttner and A. Asam J. Organomet. Chem. 1993 447,71. 21 M. Weiber and N. Graf 2.Anorg. Allg. Chem. 1993 619 1991. 20 A. Haaland H. P. Verne H. V. Volden H. J. Breunig and S. Gulec Z. Naturforsch. Teil B 1993,48 1065. 29 P. P.Paul T.B. Rauchfuss and S.R. Wilson J.Am. Chem. SOC. 1993 115 3316. 30 C. J. Warren D. M. Ho R.C. Haushalter and A. B. Bocarsly Angew. Chem. Int. Ed. Engl. 1993,32,1646. 31 W.-W. du Mont and T. Severengiz Z. Anorg. Allg. Chem. 1993 619 1083. 32 M. Baudler P. Koch and Ch. Wiaterek Z. Anorg. Allg. Chem. 1993,619 1973; F. Frick and M. Jansen ibid. 1993 619 281. 33 P.G. Jones and A. Weinkauf Acta Crystallogr. Sect. C 1993 49 1810. 34 W.S. Sheldrick and T. Hausler Z. Naturforsch. Teil B 1993 48 1069. 35 H. Jun and R. J. Angelici Organometdlics 1993 12 4265. D.A. Armitage The l-molybda-2-phospha-1,3-diene chelate of the iron complex (4)reacts with PhC-CH to give the iron-substituted cyclobutene derivative (5) (Equation 3).36 Titanacycles (6)function as C-equivalents in their reaction with aryl aldehydes giving allenes as products (Equation 4).37 mes*PHCl eliminates Ph,P/HCl from A5-phospha-allenes (7) and A5-phosphabuta- triene (8) to give the appropriate A3-derivative (Equation 5).38 The p-dimethyl- aminophenyl derivative of (8; R' = R2= p-Me,NC,H,) readily oxidatively couples to the diph~sphine.~~ Ph,P=C=C=CR'R2 (8) Ph3P=C=CPhz (7) WS*P=C=C=CR'R~ -mes'P(H)CI c mes'P=C=CPh Unsubstituted 1-and 2-phosphabutadienes result through 1,4-and 1,2-HC1 elimination and have been confirmed by trapping (Equations 6 and 7).40 CICH=CH4H2PH2 -HC=CH-CH=PH (6) CICH2PHCH=CHZ c HZC= P-CHSH? (71 Coupling mes*P(H)Li(dme)X with PhC-CPh generates the 1-phospha-ally1 anion (9) which shows a short P-C bond of 175.7pm with a terminal phenyl group in the plane of the phospha-ally1 group and orthogonal to the other two aryl rings (Equation 36 H.Lang M. Leise and L. Zsolnai J. Organornet. Chem. 1993 447 C1. '' K. A. Hughes P. G. Dopico M. Sabat and M.G. Finn Angew. Chern. Int. Ed. Engl. 1993 32 554. 38 G. Markl and W. Bauer Tetrshedron Lett. 1993 34 2915. 39 G. Markl P. Kreitmeier and R. Daffner Tetrahedron Lett. 1993 34 7045. 40 J.-C.Guillemin J.-L. Cabioch X. Morise J.-M. Denis S. Lacombe D. Gonbeau G. Pfister-Guillouzo P. Guenot and P. Savignac Inorg. Chern. 1993 32 5021. N P As Sb and Bi 8).41 The cyclopropenylphosphane (10) reacts with isocyanates RNCO where R = Ph naphthyl or But to give adducts which after the elimination of siloxane in the presence of OH - yield 1 -aza-3-phospha-allenes (Equation 9).42 3 ,0SiMe3 a (9) P(SiMe& P'C P=C=NR NRSiMe Metallating C-chloro-diphosphiranes with Mo W or Co carbonyl anions provides a route to both 0-and n-diphospha-ally1 complexes while with C-dichloro-diphos- phiranes the 1,3-diphospha-allene is formed.43 Calculations suggest that the dimerization of HCEP head to head is inherently favoured over head to tail by some 37 kJ mol-',such that formation of the latter must be sterically ~ontrolled.~~ BUT-P bonds y~' and q2 to transition metal residues through the reaction with Pt(dppe) and then with M(CO),THF (M = Cr Mo W) (Equation BU'CPP Wdppe) -P R=Cy Ill C But (CO),Mn[SPR,] adds to Bu'C-P to give l-thia-2,4-diphospholes (Equation 1l).46 4- and 8-Phosphathiophenetriptycenes and 4,s-diphosphathiophentryptycenesreadily complex metal pentacarbonyl residues.47 Coupling Ph,PC-CPPh with Ph2PK leads to Ph4P and the cumulene 41 E.Niecke M. Nieger and P. Wenderoth J. Am. Chem. SOC. 1993 115 6989. 42 T. Wegmann M. Hafner and M. Regitz Chem. Ber. 1993 126 2525. 43 R. El-Ouatib D. Ballivet-Tkatchenko,G. Etemad-Moghadam and M. Koenig J.Organomet. Chem. 1993 453 77. 44 M.T. Nguyen L. Landuyt and L. G. Vanquickenborne J. Org. Chem. 1993 58 2817. 45 D. Carmichael S. I. Al-Resayes and J. F. Nixon J. Organomet. Chem. 1993 453 207. 46 E. Lindner C. Haase H. A. Mayer M. Kemmler R. Fawzi and M. Steimann Angew. Chem. Int. Ed. Engf. 1993 32 1424. 41 A. Ishii I. Takaki J. Nakayama and M. Hoshino Tetrahedron Lett.1993,34,8255;A. Ishii R. Yoshioka J. Nakayama and M. Hoshino ibid. 1993 34 8259. D.A. Armitage (Ph,P),C=C=C=C(PPh,) which readily adds sulfur and shows alternating C-C bond lengths.48 Fe (CO),dechlorinates R(Cl)PCH,Cl to give the phospha-alkene cluster [(,u3,q2-RP=CH ,)Fe3 (CO) J,while with Fe,(CO) ,the phosphinidene phospha-alkene cluster [(p3,q2-RP=CH,)(,u3-PR)Fe3(CO)g] results.49 Both metal-atom/ligand vapour co-condensation and ligand substitution with phosphabenzene at bis(2,4-dimethyl-q5-pentadieny1)Cr give hexakis(q'-phos-phinene)Cr. The Cr-P bonds are particularly short as suggested by a bathochromic shift in the MLCT region of the UV/visible ~pectrum.~' With Os,H,(CO),, C,H,P behaves as an q3-ligand (the structure of the 2-t-butyl derivative supports this assignment) while a product with two phosphabenzene rings coupled through positions 1 and 2 also res~lts.~' Organic azides oxidize phosphabenzenes to cyclodiphospha-(v)-azanes,52(0-Ar-C=CAr)PHAr' condenses to the phosphindole and the bisphosphorane PhC=CPPh,C=CPPh,C-CPh has been prepared.' Pr',PX adds to ynamines to give the phosphirene exclusively for X = Br I but provides the first example of ring-chain tautomerism with the P-substituted enamine if X = C1 (Equation 12).54 5 Phosphorus-Nitrogen Compounds mes*N=PCl reacts with Cp,ZrMe through insertion into the Zr-Me bonds to give (11)which isomerizes to (12) (Equation 13).55 Reacting mes*N=PCl with GaCl in arene solvents gives [mes*N=P] (arene)X-1 + (X = GaCl or Ga,Cl,) in which phosphorus interacts with arene and the anions with P-N bonds of 146-148 The cation adds to R,N-P=NBu' and alkyl azides 48 H.Schmidbaur S. Manhart and A. Schier Chem. Ber. 1993 126 2389. 49 D. J. Brauer A. Ciccu J. Fischer G. Hessler 0.Stelzer and W. S. Sheldrick J. Organomet. Chem. 1993 462 111. so C. Elschenbroich M. Nowotny J. Kroker A. Behrendt W. Massa and S. Wocadlo J.Organomet. Chem. 1993,459 157. 51 A. J. Arce A. J. Deeming Y. De Sanctis and J. Manzur J. Chem. SOC.,Chem. Commun. 1993 325. 52 G. Markl H. Sommer and H. Noth Tetrahedron Lett. 1993 34 3107. 53 G. Markl G.Y. Jin and K.-P. Berr Tetrahedron Lett. 1993 34 3103; S. Ogawa Y. Tajiri and N. Furukawa ibid. 1993 34 839. 54 N. V. Lukashev P. E. Zhichkin M.A. Kazankova and I. P. Beletskaya Tetrahedron Lett. 1993,34 1331. 55 A. Igau N. Dufour A. Mahieu and J.-P. Majoral Angew. Chem. Int. Ed. Engl. 1993 32 95. 56 N. Burford J.A.C. Clyburne P.K. Bakshi and T.S. Cameron J. Am. Chem. SOC. 1993 115 8829. N P,As Sb and Bi 61 providing a route to P-N heterocycle^.'^ Both 1,8-diazabicyclo[5.4.O]undec-7-ene (DBU) and 1,5-diazabicyclo[4.3.O)non-5-ene (DBN) react with (PriN),PCl and PriNPCl as strong nucleophiles to give salts of the cations [(PriN),PLJ+ and [Pr\NPL2I2+ which are isolable as crystalline PF derivatives.’* The phosphenium + salt [ClP=NR] reacts with guanidines (R,N),C=NSiMe to give P-N hetero-cycle~.~~ Reacting CoC1 with LiN(PPh,) gives the cyclophosphazane complex (13) and N(PPh,) and is formed through oxidative scrambling of the original anion to give the intermediate nitrene Ph,P-N which adds to this anion (Equation 14).60 N-p ,P-N> %GI2 + GL~N(PPII~)~-p,42p + 2(Ph2P)3N + Xo + 6LiCI N,/ P-N P (14) (13 Ph groups omittedfor clarity) The iodide (mes*N=),P-I results from mes*N=PN(mes*)SiMe through oxidation by chlorine or bromine loss of Me,SiX and exchange with Me,SiI.It shows planar coordination about P and orthogonally arranged mes* rings.61 The triphosphazane (CF,),P=N=P(CF,),=N=PPh results from the reaction of (CF,),PN and (CF,),P=N=PPh and bonds in monodentate fashion to the Os,(CO) cluster through the terminal P atom. The structural determination of the ligand and complex shows a highly delocalized P=N=P=N=P system.62 Further studies of the phosphazene superbases [(Me,N),P=N-P(NMe,),=N],P=NBu‘ and their oligomers give pK,,+ values in MeCN of 43 to 47.63 6 Arsenic and Antimony-Nitrogen Coupling ArNH (Ar = 2,6-PriC6H,) with AsCl gives dimeric (ArNHAsNAr) which with M[N(SiMe,),] (M = Zn Cd) forms the amide complexes of the two metals with distorted tetrahedral c~ordination.~~ Ph,P is oxidized by (CF,),AsN to give the arsinophosphazene (CF,),As-N=PPh which has a P=N double bond and As-N bond which is much shorter than single.The As-N bond shortens on coordination in osmium carbonyl cl~sters.~’ Sb(N=CPh,) shows pyramidal ge- ometry and short intermonomer (326 pm) aromatic-meta-C-H --Sb interactions.66 7 Catenation and Clusters The diphosphene (14)on oxidation with PCl gives the diphosphine which cyclizes 57 G.David E. Niecke M. Nieger V. von der Gonna and W. W. Schoeller Chem. Ber. 1993 126 1513. ’*R. Reed R. Reau F. Dahan and G. Hertrand Angew. Chem. Int. Ed. Engl. 1993 32 399. 59 V. D. Romanenko T. V. Sarina M. Sanchez A. N. Chernega A. B.Rozhenko M.-R. Mazieres and M. I. Povolotski J. Chem. SOC.,Chem. Commun. 1993 963. 6o J. Ellerman J. Sutter F.A. Knoch and M. Moll Angew. Chem. Int. Ed. Engl. 1993 32 700. 61 A. Ruban M. Nieger and E. Niecke Angew. Chem. Int. Ed. Engl. 1993,32 1419. 62 H.G. Ang Y. M. Cai and W. L. Kwik J. Organomet. Chem. 1993,448 219. 63 R. Schwesinger C. Hasenfratz H. Schlemper L. Walz E.-M. Peters K. Peters and H. G. von Schnering Angew. Chem. Int. Ed. Engl. 1993 32 1361. 64 U.Wirringa H. W. Roesky M. Noltemeyer and H.-G. Schmidt Angew. Chem. Int. Ed. Engl. 1993 32 1628. 65 H.G. Ang W. L. Kwik Y. W. Lee and A. L. Rheingold J. Chem. SOC.,Dalton Trans. 1993 663. 66 A. J. Edwards M. A. Paver P. R. Raithby C. A. Russell and D. S. Wright J. Chem. SOC.,Dalton Trans. 1993 2257. D. A. Armitage with base subsequent alkylation leading to formation of the diphosphene imine where for R = Bu' the P=N and P=P bonds are 155 and 203.6 pm respectively indicating multiple bond character (Equation 15).67 Prnes' /r Butp//Pmes' mes'NHP=Prnes' CI-P'I 2Bd-p (14) \Nmes* \Nmes* 'Nmes' (15) The diphosphene (E)-mes*P=PIs results from mes*PHLi and IsPX and isomer- izes to the (Z)-isomer with an activation energy of 29.5kcalmol-' (providing the n-component of the double bond).Other products include P-substituted indanes.68 The metallodiphosphenes [(q5-L)(CO),Fe-P=P-mes*] (L = substituted cyclopen- tadienyl) complex CT to the Cr(CO) residue but n to Pt(PPh,),.69 1,3-Bu~C,H,Ta(CO),[LTa(CO),] on heating with P gives the complex [L3Ta,(p3- P4)(p3-P2)] which reacts with Fe,(CO) to give the Fe(CO) adduct. The P(P) unit caps the three Ta groups while the P unit coordinates phosphinidene to one Ta and bridges phosphido to the other pair.70 The cyclopentazole ion N; is unstable relative to N3 and N, although a 19.4kcal mol- ' activation energy inhibits decomp~sition.~' Pi is stable to dissocia- tion and disprop~rtionation.~' Reductively coupling Cr(CO),PCl with CpMo(C0); gives CpMo(CO),P, while 1,3-Bu\C5H,Fe(CO); yields 1 ,~-Bu\C,H,F~P,.~~ Fe is extruded from Fe(qS-P,C,Bu:)(q5-P,C,Bu:) using Ru,(CO), to give the phos- phino-phosphinidene cluster Ru (CO) (P,C Bu:).Heating the elements Ba and P to 1490 K in a 4 :3 ratio gives Ba,P which contains P:-and P3 -ions the former as two crystallographically independent dumb-bell anions with bond lengths of 225 and 232~m.~~ The Zintl phase Na8TiAs contains TiAs tetrahedra while calculations show P8 to be most stable as a cuneane str~cture.~' BuLi and P2H4 give LiH,P among the first reaction products. It also results from Li,P7 or LiH,P with P,H,.76 HP reacts with zirconacene derivatives as a monodentate and chelating ligand while P gives the q4-complex Bu:C,H3Co(q4- P4)[Cr(C0),I3 in which the P unit is planar and caps the Co atom and Bu;C,H,M(CO) (M = Nb Ta) gives some P,and P complexes.77 The phosphinidene cluster Fe,(CO),(p-PH) results from hydrolysis of 67 E.Niecke B. Krarner M. Nieger and H. Severin Tetrahedron Lett. 1993 34 4627. " C. M. D. Kornen F. J. J. de Kanter S.J. Goede and F. Bickelhaupt J. Chem. SOC.,Perkin Trans. 2 1993 807. 69 L. Weber I. Schurnann H.-G. Starnrnler and B. Neurnann J. Organomet. Chem. 1993 443 175. 70 0.J. Scherer R. Winter and G. Wolrnershauser J. Chem. SOC. Chem. Commun. 1993 313. 71 M.N. Glukhovtsev P. von R. Schleyer and C. Maerker J. Phys. Chem. 1993 97 8200. '' M. Scheer G. Friedrich and K. Schuster Angew. Chem. Int. Ed. Engl. 1993 32 593. 73 R. Bartsch P. B. Hitchcock and J.F. Nixon J.Chem. SOC. Chem. Commun. 1993 311. 74 C. Hadenfeldt H.-U. Terschuren W. Honle L. Schroder and H. G. von Schnering Z. Anorg. Allg. Chem. 1993 619 843. 75 J. Stuhrrnann A. Adam and H.-U. Schuster Z. Naturforsch. Teil B 1993,48,898;B. M. Girnarc and D. S. Warren Inorg. Chem. 1993 32 1850. 76 M. Baudler R. Heurnuller and D. Duster Z. Anorg. Allg. Chem. 1993 619 1007. 77 M. Baudler and B. Wingert 2.Anorg. Allg. Chem. 1993,619 1977; M. Scheer U. Becker J.C. Huffrnan and M. H. Chisholrn J. Organomet. Chem. 1993,461 C1; 0.J. Scherer R. Winter and G. Wolrnershauser Z. Anorg. Allg. Chem. 1993 619 827. N P,As Sb,and Bi Fe,(CO),(p,-PSiPr',) and as its dianion functions as a good cluster building reagent.78 Heating [CpCr(CO),] with P gives clusters containing P, P, and PI residues while [Cp*Co],As inserts Mo(CO), using Mo(CO),thf to give [C p *Co] ,Mo(C0),As6.The first stibacumulenium ion results from [Me,C,Cr(CO),] ,SbC1 and GaCl (Equation 16) while K,Sb and (Ph,P),Ni(CO) give Sb,Ni,(CO);- as a nido 10-vertex cluster.80 8 Nitrogen Methylation of ONCl with MeOSO'MF; (M = As Sb) gives the nitryl cation ON(C1)Me+ (isoelectronic with acetyl chloride) protonation of CF,NO gives CF,N(O)H+ and CF,NH,OH+ salts using the super-acid system HF/MF, while Cl,CNH=CCl~SbCl; shows a planar cation skeleton with C-N bond lengths of 148.8 and 128.0pm.81 A range of rhenium imines and nitrides have been prepared. The imide-bridged complex Tc,(NAr),(p-NAr) can be terminally methylated with MeMgCl to give Tc,(NAr),(p-NAr),Me in which two methyl groups substitute a terminal NAr group.8 Reacting [V(mes),(thf)] with Na under N fixes the nitrogen as the anionic species [(mes),V(p-N,)(p-Na)V(rnes),]-and gives NH and N2H4 on protoly~is.~~ The trans-diazene complex [trans,trans-W(HN=NH)(CO),(NO)(PR,),Iis obtained oia the + hydrazine complex through oxidation with P~(OAC),.~ [WCl,(NNPh,)(PMe,Ph),] protolyses to diphenylamine and ammonia with the former as the main product and various rner,trans-[WX,(NN=CR,)(PR,),] complexes have been prepared.85 Fe,(CO) and PhN give the bridged complex [Fe,(CO),(p-Ph,N,)] (15) which reacts with CO and H to give the insertion and reduction products [Fe,(CO),(p- PhNCONPh)] and [Fe,(CO),(p-NHPh),] via N-N cleavage.Complex (15) also undergoes cage expansion with Fe,(CO) to give the p3,q2cluster [Fe,(CO),(NPh),] which isomerizes in solution with N-N cleavage to give the bis-p bridged cluster.86 H,NNH-and H,NO-give q2-complexes with the tripod-Co residue 78 M.T.Bautista M. R. Jordan P.S. White and C. K. Schauer Znorg. Chem. 1993 32 5429. L. Y. Goh R. C. S. Wong and E. Sinn Organometallics 1993,12,888;M. Detzel K. Pfeiffer 0.J. Scherer 79 and G. Wolmershauser Angew. Chem. Int. Ed. Engl. 1993 32. 914. 80 F. Bringewski G. Huttner and W. Imhof J. Organomet. Chem. 1993.448,C3;S. Charles B. W. Eichhorn and S. G. Bott J. Am. Chem. Soc. 1993 115 5837. 81 R. Minkwitz and D. Lamek Z. Anorg Allg. Chem. 1993,619 1743; R. Minkwitz H. Preut M. Seifert and D. Lamek Z.Naturjiorsch. Teil B 1993 48 1241; R. Minkwitz D. Lamek and H. Preut ibid. 1993,48 1075. 82 R. Rossi A. Marchi L. Marvelli L. Magon M. Peruzzini U. Casellato and R. Graziani d. Chem. SOC. Dalton Trans. 1993 723; A. K. Burrell and J. C. Bryan Organometallics 1993 12 2426. n3 R. Ferguson. E. Solari C. Floriani A Chiesi-Villa and C. Rizzoli Angew. Chem. Int. Ed. Engl. 1993.32 396. n4 M.R. Smith 111 T.-Y. Cheng and G.L. Hillhouse J. Am. Chem. Soc. 1993 115 8638. 85 J. R. D. De Bord T.A. George Y. Chang Q. Chen and J. Zubieta Inorg. Chem. 1993,32,785;H. Oshita Y. Mizobe and M. Hidai J. Organomet. Chem. 1993 461 43. 86 B. Hansert and H. Vahrenkamp J. Organomet. Chem. 1993 459 265; ibid. 1993 460,C19. 64 D. A. Armitage + MeC(CH,PPh,),Co2 .87 Photolysis of l-thia-3,4-diazolidine gives cis-di-imide which readily hydrogenates multiple bonds.87 The aminodiazonium cation H,Nl has been isolated as salts using HN in HF.The structure has been determined at 20 K as [H,N-N=N]+ with almost linear N-N bonds of 129.5 and 110.1 pm.88 N40 results from the reaction NOCl and NaN, it has a bent structure (determined from vibrational spectra and calculations) and is NO singly bonded through nitrogen to a terminal nitrogen atom of the almost linear azido The penta-azadienide anion [tolN=N-N-N=Ntol] -forms salts with terminal N-N bonds of about 128 pm and inner ones of 134 pm in the [Cs,(18-crown-6)]2~complex, but it is more delocalized in [(NH4)[Cr(NH,),(H,0),](tolN,tol),] with cations and anions hydrogen-bonded to each other." The nitrides M,[TaN,] (M = Sr Ba) show polymeric bridged tetrahedral chains while M,[MnN,] have trigonal planar D, anions." 9 Phosphorus and Arsenic PH is produced biogenetically in the rumen gut and manure of cattle its concentration increasing along the digestive tract.92 The lithium phosphide Li(DME) PBui crystallizes as a dimer with Li,P bridges while Li(DME)PPh is polymeric with Li-P bridges.' Tris(8-dimethylamino-1-naphthy1)phosphaneshows weak N - - P interactions of 280 to 285 pm while those in tris[2-(dimethylaminomethyl)phenyl]phosphane show rather weaker N--P interactions of 299 to 307pm.The latter is methylated at nitrogen using Me1 but the former methylates at phosphorus indicating the stronger N -P interaction and suggesting ~even-coordination.~~ The strong base P(MeNCH,CH,),N results from the reaction of (HMeNCH,CH,),N with ClP(NEt,) and Bu'OK in 81% yield in a one-pot synthesis while 1,3,5-triaza-7- phospha-adamantane an air-stable phosphine readily complexes with metal carbonyl residues.95 While Me,BPR (R = But and SiMe,) and Et,BP(SiMe,) are colourless dimeric solids Et,BPBu\ is the first monomeric tetra-alkyl phosphinoborane as a volatile yellow liquid.Both (mesBPBu') and (mesBPBu') form complexes with carbonyls which are best considered as nido complexes with the BP residue as a square or hexagonal-pyramidal str~cture.~~ Phosphino and arsinoalanes can be base stabilized '' S. Voge1,G. Huttner L. Zsolnai and Ch. Ernmerich Z. Naturforsch.Teil B,1993,48,353;M. Squillacote J. De Felippis and Y. Lai Tetrahedron Lett. 1993 34 4137. '' K. 0.Christe W. W. Wilson D. A. Dixon S. I. Khan R. Bau,T. Metzenthin,and R. Lu,J. Am. Chem. Soc. 1993 115 1836. 89 A. Schulz I.C. Tornieporth-Oetting and T. M. Klapotke Angew. Chem. Int. Ed. Engl. 1993 32 1610. 90 S. Dieterich and J. Strahle 2. Naturforsch. Teil B,1993 48 1574. 91 A. Tennstedt C. Rohr and R. Kniep Z. Naturforsch. Teil B,1993,48 794; F.K.-J. Helrnlinger P. Hohn and R. Kniep ibid. 1993 48 1015. 92 G. Gassrnann and D. Glindernann Angew. Chem. Int. Ed. Engl. 1993 32 761. 93 G. Stieglitz B. Neurnuller and K. Dehnicke Z. Naturforsch. Teil B,1993 48 156. 94 C. Chuit R. J. P. Corriu P. Monforte C. Reye J.-P. Declercq and A. Dubourg Angew. Chem.Znt. Ed. Engl. 1993 32 1430. 95 J.-s. Tang and J.G. Verkade Tetrahedron Lett. 1993 34 2903; E.C. Alyea K. J. Fisher S. Foo and B. Philip Polyhedron 1993 12 489. 96 T.J. Groshens K. T. Higa R. Nissan R. J. Butcher and A. J. Freyer Organometallics 1993 12 2904; B. Kaufrnann H. Noth R.T. Paine K. Polborn and M. Thornann Angew. Chem. Znt. Ed. Engl. 1993 32 1446. N P As Sb and Bi as H,AlEMes,.NMe, but give the trimer on heating with loss of base (H,AlEMes,) (E = P As). Adding primary phosphines or arsenines to BuiM (M = Ga Al) affords the bridged dimers and trimers [Bu\M(p-EHBu')] (E = P As; n = 2,3).97 The structure of Pr',AsBmes shows the As-B bond to be 201.9pm tending to support n-bonding and is considered to be present in [mes,BAsPh]- and highly hindered arsinoboranes .'* 10 Bismuth Structure determinations supported by calculations suggest a trigonal bipyramidal structure for Me,Sb which is some 7.1 kJ mol- 'more stable than the square pyramidal structure.Similar calculations support such a structure for the unknown Me5Bi." With Ar,Bi however a square pyramidal structure is usually adopted and these compounds are intensely coloured due to charge-transfer. Ph,Bi reacts with PhLi to give the hexacoordinate anion Ph,Bi -as yellow crystals and has an octahedral-like structure (close to T symmetry) with opposite phenyl groups almost coplanar. It also gives a blue 1 1 complex with pyridine."' Irradiating Ar,Bi(N,) in the presence of alkynes provides a route to N-unsub- stituted 1,2,3-triazoles.Oxidizing Ph,Bi with ozone in toluene gives surprisingly triphenylbismuth diformate which on treatment with halides gives Ph,BiX,."' Ar,BiF couples with silyl ethers to give (2-oxoalkyl)triarylbismuthoniumsalts and CF,SO,N(SiMe,) to give bismuth imines."' Reducing 1-phenyl-2,5-dimethylbismolewith Li followed by coupling with Mn(CO),Br gives the a-complex (16) which on melting loses CO to form the q5-derivative (17) (Equation 17).'03 The complex [Ph,Bi(HMPA),] '[BF,] -results from Ph,BiBr/AgBF and HMPA. The cation has a trigonal bipyramidal structure with equatorial lone pair and phenyl 97 D. A. Atwood A. H. Cowley P. R. Harris R. A. Jones S. U. Koschmieder and C. M. Nunn,J. Organomet. Chem. 1993 449 61; D.A. Atwood L. Contreras A.H. Cowley R.A.Jones and M.A. Mardones Organometallics 1993 12 17. 98 M. A. Mardones A. H. Cowley L. Contreras R. A. Jones and C. J. Carrano J. Organomet. Chem. 1993 455 C1; M. A. Petrie M. M. Olmstead H. Hope R. A. Bartlett and P. P. Power J.Am. Chem. SOC.,1993 115 3221. 99 A. Haaland A. Hammel K. Rypdal 0.Swang J. Brunvoll 0.Gropen M. Greune and J. Weidlein Acta Chem. Scad. 1993,47 368. loo S. Wallenhauer D. Leopold and K. Seppelt Inorg. Chem. 1993 32 3948. lo' H. Suzuki C. Nakaya and Y. Matano Tetrahedron Lett. 1993 34 1055; H. Suzuki T. Ikegami Y. Matano and N. Azuma J. Chem. SOC. Perkin 1 1993 2411. lo' Y. Matano N. Azuma and H. Suzuki Tetrahedron Lett. 1993,34,8457; S. V. Pasenok N. V. Kirij Y. L. Yagupolskii D. Naumann and W. Tyrra J. Fluorine Chem.1993 63 179. '03 A. J. Ashe 111 J. W. Kampf and D. B. Puranik J. Organomet. Chem. 1993,447 197. D.A. Armitage groups.'04 Tris(2-methoxy- or 2,6-dimethoxyphenyl)bismuth,on heating with amines or alcohols in the presence of carboxylic acids RCH,CO,H bearing a-hydrogen readily gives the corresponding amide or ester.lo5 Bi[OCH(CH3)J3 and Bi[OC,F,] occur as solvated bridged dimers in THF,' O6 while tris(2-ethylhexy1)phosphate provides for the separation of bismuth(II1) from solutions containing lead antimony gold and tell~rium.'~~ Io4 C.J. Carmalt N. C. Norman A.G. Orpen and S. E. Stratford J. Orqanomet. Chem. 1993 460,C22. Io5 T. Ogawa T. Hikasa T. Ikegami N. Ono and H. Suzuki Chem. Lett. 1993 815. lo6 C. M. Jones M. D. Burkart R.E. Bachman D.L. Serra S.-J. Hwu and K. H. Whitmire Znorq. Chem. 1993 32 5136. lo' A. D. Barve G.S. Desai and V. M. Shinde Bull. Chem. Soc. Jpn.. 1993 66,1079.

ISSN:0260-1818    

DOI:10.1039/IC9939000055

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

0,S Se and Te By J. D. WOOLLINS Department of Chemistry Loughborough University of Technology Loughborough LEI 1 3TU UK An excellent monograph on oxygen chemistry which includes a vast quantity of thermodynamic and related data as well as a very extensive account of the reaction chemistry of dioxygen was published.’ In addition interesting reviews on singlet oxygen, 0,O’chelates of Si Ge and Sn3 and a monograph on transition metal oxides4 as well as a compilation of phase diagrams of the elements’ were also published. Reviews on homo- and hetero-atomic chalcogen rings, Te-N and Se-N compounds’ and the coordination chemistry of heavy polychalcogenide ligands8 illustrate just how active research in these areas has become in recent times. A number of computational and fundamental spectroscopic studies were carried out.Thus MO calculationsg suggest that the neutral SO molecule (previously claimed to be formed upon photolysis of 03/S03in an Ar matrix at 15 K) contains an SO ring and has C, symmetry. The species S203is predicted to have a three-membered S,O ring although no suggestions as to preparative routes were made. Some interesting predictions about geometries of h yperlithiated main groups species were also made,’ for example SLi is expected to consist of two SLi rings fused at sulfur. A number of fundamental spectroscopic studies have been reported. For example,’ the protonation of oxocarbon systems in magic acid (SbF3/FS03H) was studied by 13C NMR with the results being correlated with ab initio/IGLO calculated data to gain insight into the species present in solution.The l80isotope shift enabled the coupling constant between the carboxyl carbons of succinic acid to be determined;’ 53% l80 labelled dimethylmaleic anhydride gives eight I3C signals in the carbonyl and olefinic regions which can be interpreted in terms of isotope shifts over one two and even three D.T. Sawyer ‘Oxygen Chemistry’. International Series of Monographs on Chemistry. Oxford University Press 1993. E.A. Lissi M. V. Encinas E. Lemp and M.A. Rubio Chem. Rev. 1993 93 699. C.Y. Wong and J. D. Woollins Coord. Chem. Rev. 1994 130 175. P. A. Cox ‘Transition Metal Oxides. An Introduction to their Electronic Structure and Properties’. International Series of Monographs on Chemistry Oxford University Press 1993.’ D. A. Young ‘Phase Diagrams of the Etlements’. University of California Press 1993. R. S. Laitinen P. Pekonen and R. J. Suontamo Coord. Chem. Rev. 1994 130 1. ’ A. Haas and J. Kasprowski Coord. Chem. Rev. 1994 130 301. * M.G. Kanatzidis and S.-P. Huang Coord. Chem. Rev. 1994 130 509. M.L. McKee J. Am. Chem. SOC.,1993 115 9136. lo J. Ivanic C.J. Marsden and D. M. Hassett J. Chem. SOC.,Chem. Commun. 1993 822. ‘I G. A. Olah J. Bausch G. Rasul H. George and G. K. S. Prakash J. Am. Chem. SOC.,1993 115 8060. l2 T.L. Mega and R.L. Van Etten J. Am. Chem. SOC. 1993 115 12056. 67 68 J.D.WooEIins bonds. le3W NMR was used13 to characterize a-[H,WllV040]7-and a-CH2W11 Mo0,0I6 -* A number of interesting reactions involving 0x0-species were reported.Thus the peroxynitrite anion ONOO- (which has roles in biology and in nitrate photolysis) was prepared by reaction of HOO- with alkyl nitrites,I4 Equation 1. RON0 + HOO-+ ROH + ONOO-(1 1 The photochemical decomposition of halogen oxides plays an important part in the destruction of the stratospheric ozone of the Antarctic. The photodecomposition of OClO to give atomic chlorine has been studied." Sulfur-oxides are also important environmentally; with the oxidation of HSO being important in flue gas desulfuriz- ation. It has now been proposed16 that HSOS is present as an intermediate in the oxidation of HSO by 0,.A matrix isolation photochemistry study17 has shown that SBrF may be obtained by UV photolysis of FC(0)SBr.According to IR studies short UV irradiation times leads to the formation of both conformers of FC(O)SBr but longer exposure gives SBrF. Organometallic and coordination compounds containing oxygen and 0 donors continue to be of interest. A reinvestigation of the IR spectra of oxoosmium(v1) esters was reported." A metastable rhodium dioxygen complex was de~cribed.'~ Photo-chemically activated reaction of RhCl(CO)(PPh,) [v(CO) 1980 cm- '] with singlet oxygen at low temperature gave Rh(0,)Cl(CO)(PPh3)z [v(CO) 2044cm- ' v(00) 901 cm- '3 which is stable in solution below 0 "C; the difference in v(C0) between the starting material and product suggests that the peroxo complex is very electron poor. A dioxygen complex of molybdenum porphyrin [M~'~O(tmp)] (H,tmp = 5,10,15,20-tetramesitylporphyrin) was described." Introduction of 0 gives [M~'~O(O,)(trnp)] [v(OO) 928 cm- '3 which on irradiation with visible light i,eleases oxygen according to Equation 2.[Mo'"O(tmp)] + Oz-[M0'~0(O,)(tmp)] (2) Related to the above work a study of the photochemistry of peroxotitanium(1v) tetraphenylporphyrin revealed" that irradiation of Ti(O,)(tpp) results in cleavage of the 0-0 bond and formation of TiO(tpp0) (Figure 1) which undergoes further photodecomposition to give TiO(tpp). The first crystallographic characterization of the V0Cl:- (Figure 2) anion obtained" from the ambient temperature ionic liquid [enim]Cl-AlCl (enim = 1-ethyl-3-methylimidazolium cation) was described. Reaction of Na,Mo04 with FeS in water gave Na6[H6Mo,7Fe,0,83(NO)6(HzO)18].91H,O a new polymetallate cluster.23 The X-ray determination showed the compound to consist of three l3 J. J. Hastings and 0.W. Howarth Polyhedron 1993 12 847. l4 J. R. Leis M. E. Pena and A. Rios J. Chem. SOC.,Chem. Commun. 1993 1298. R.C. Dunn J. L. Anderson C.S. Foote and J. D. Simon J. Am. Chem. SOC. 1993 115 5307. l6 R.E. Connick S.Lee and R. Adamic Inorg. Chem. 1993 32 565. C.O.D. Vedova and H.-G. Mack Inorg. Chem. 1993 32 948. D.V. McGrath G.D. Brabson K. B. Sharpless and L. Andrews Inorg. Chem. 1993 32 4164. l9 M. Selke C.S. Foote and W. L. Karney Inorg. Chem.. 1993 32 5425. 2o J. Tachibana T. Irnamura and Y. Sasaki J. Chem. SOC.,Chem. Commun. 1993 1436. M. Hoshino K. Yarnamoto J. P. Lillis T. Chijirnatsu and J.Uzawa Inorg. Chem. 1993 32 5002. 22 P.B. Hitchcock R. J. Lewis and T. Welton Polyhedron 1993 12 2039. 23 G.-Q.Huang S.-W. Zhang and M.-C. Shao Polyhedron 1993 12 2067. 0,S Se and Te .Ph2 Ph’ Figure 1 Proposed structure of TiO(tpp0) formed from photoreaction of Ti(O,)(tpp) (tpp = tetraphenylporphyrin)2’ Figure 2 The structure of the [VOC1,]2-anion22 17-molybdate subunits connected by six FeO octahedra and three (Mo,O,} groups. An (alkylperoxo)copper(Ii) complex of copper was obtained24 by addition of excess t-butylhydrogenperoxide to the bis(p-hydroxo)copper complex [Cu(HB(3,5-Pr\pz),12 [OH] (Figure 3) the steric bulk of the tris(pyrazoy1)borate ligand appears to limit the reactivity of the coordinated alkylperoxo ligand.An interesting example of a 1,2 hydrogen migration was reportedz5 for Re(EtCCEt),(OH) which slowly rearranges to give Re(ETCCEt),(O)H and ETCCET in benzene solution; although the hydroxide rearranges to the 0x0-hydride the methoxide and phenoxide complexes appear to be stable in this respect. Rhenium is also involved in the first example of a bimetallic complex containing carbon dioxide bonded in a 0,0’-q2,q1-C fashion,26 [(dppp)(CO),ReO,CRe(CO),(dppp)] [dppp = 1,3-bis(diphenylphosphino)pro-pane]. An exciting development in systems for oxygen binding was the report on iron ‘octopus-porphyrins’ in the four alkyl phosphocholine groups on each side of the porphyrin ring plane form fibrous aggregates in aqueous solutions. Also relevant to biological inorganic chemistry was the observation of ligand induced helical bridges in dimeric lanthanide complexes;28 by using bis(pyridin-2-one) ligands a triple helical structure was obtained (Figure 4).The uranium helical polymer obtained from reaction of N,N’-ethylenebis(2-pyrrolidone) (ebpyrr) with uranyl nitrate in acetonitrile was found to form a peroxo bridged complex [(UO,)(NO,)(ebpyrr),(p-O,)] upon 24 N. Kitajima T. Katayama K. Fujisawa Y. Iwata and Y. Moro-oka J. Am. Chem. SOC. 1993,115,7872. 25 S.K. Tahmassebi R. R. Conry and J. M. Mayer J. Am. Chem. Soc. 1993 115 7553. 26 S.K. Mandal J.A. Krause and M. Orchin Polyhedron 1993 12 1423. ‘’ T. Komatsu K. Nakao H. Nishide and E. Tsuchida J. Chem. SOC.,Chem. Commun. 1993 728. D. L. M. Goodgame S. P. Hill and D. J.Williams J. Chem. Soc. Chem. Commun. 1993 1019. J. D.Woollins HB-N-N 0-R \ -0 Pi Figure 3 A copper (alky1)peroxo trispyrazoyl(b0rate) Figure 4 The triple helical structure observed in lanthanide complexes with long reach ligands*' exposure to air.,' Complexes of lanthanide chlorides with pyruvic acid semicarbazones were found to have scavenger effects on OH. and O,-. radical^.^' The molecular structure of Cp:Zr(OH),.(H,O) revealed that the water molecules hydrogen bond to the coordinated hydroxy groups. The result may go some way to rationalizing the observation that proton exchange between CpTZr(OH) and labelled water is more facile than oxygen exchange.'' In an elegant study a range of novel six- and twelve-membered silazoxy metalla- 29 G.A. Doyle D. M. L. Goodgame A. Sinden and D. J. Williams J. Chem. SOC.,Chem.Commun. 1993,1170. 30 S. Yu S. Wang Q. Luo L. Wang Z. Peng and X. Gao Polyhedron 1993 12 1093. 31 W.A. Howard and G. Parkin Polyhedron 1993 12 1253. 0,S Se and Te 71 cycles were prepared by reactions of suitable transition metal halides with o(siMe,NB~Li),.~~ Deoxygenation of oxovanadium(1v) complexes using carboxylic acid halides was reported for a range of vanadium complexes.33 Oxidation reactions were studied by a number of groups. Thus complexes of the type Fe"L (where L = ligands such as EDTA) bind NO in aqueous solution to give FeL(N0); these nitrosyl complexes react with sulfur(1v)oxides to give Fe"'L(N,O) sulfate and nitrogen-sulfur oxides.34 Peruthenates continue to excite as oxidation catalysts.Thus a range of alcohols aldehydes and related substrates were oxidized3' using [RuO,] -and bromate at pH 11. Barium ruthenate was reported to oxidize alkanes in acetic acid/dichloromethane with the rates of reaction being enhanced by the presence of Lewis a~ids.~~,~~ Oxidation of alkanes and alkenes were also reported3* to be efficient at 1 atm using copper catalysts such as Cu(OH),. The non stereospecific nature of the epoxidation of the alkenes suggests that these reactions involve active copper sites and are not simply due to peracids formed in situ. Platinum metal was found to have potential for similar reactions3 at elevated pressures thus in aqueous-medium ethylene and propene were oxidized to ethane-l,2-diol/acetic acid and propan- 1,2-diol and acetone respectively; although if the reactions were performed in the presence of CO only the diols were formed.The molybdenum complex [Mo(O)(O,)(H,O)(hmpa)] (hmpa = hexamethylphosphorictriamide) has found util- ity in the catalytic oxidation of aromatic amines to the corresponding nitroso with H,O being the oxidant with yields of up to 80%. Copper macrocyclic complexes have also found application for the oxidation of hy-droquinones ascorbic acid and related systems in the presence of 0 with turnover numbers of 5-20 h-';a catalytic scheme (Figure 5) based on the initial Cu' species was propo~ed.~' Related to this work studies on the mechanism of oxidation of biological substrates by Cr"' were reported.42 Although not strictly in the remit of this review an interesting 'oxidation' using the novel oxidizing agent AsPh312 was described.43 Finally in this section the light induced oxygen incision of c60 to give C6,0 was to occur with excited molecular oxygen (lo2) generated by c6 triplet energy transfer with 302.A number of studies upon small sulfur-containing systems were reported. For example reaction of S7C12 with mercury thiocyanate was shown4' to give (Equation 3) S,(CN) which consists of an S chain endcapped with CN groups with the overall molecular geometry being approximately Ci; this structure may be a reasonable model 32 A. J. Elias H. W. Roesky W. T. Robinson and G. M. Sheldrick J. Chem. SOC.,Dalton Trans. 1993 1217. 33 J.G. Reynolds E.L. Jones J. C. Huffman and G. Christou Polyhedron 1993 12 407. 34 V. Zang and R. van Eldik J. Chem. SOC.,Dalton Trans. 1993 111. 35 A. J. Bailey W. P. Griffith S.I. Mostafil and P.A. Sherwood Inorg. Chem. 1993 32 268. T.-C. Lau and C.-K. Mak J. Chem. SOC. Chem. Commun. 1993 766. 37 D. Klissurski V. Rives N. Abadzhjieva Y. Pesheva P. Pomonis T. Sdoukos and D. Petrakis J. Chem. SOC. Chem. Commun. 1993 1606. 3R S.-I. Murahashi Y. Oda T. Naota and N. Komiya J. Chem. SOC.,Chem. Commun. 1993 139. 39 M.A. Benvenuto and A. Sen J. Chem. SOC.,Chem. Commun. 1993 970. 40 S.Tollari M. Cuscela and F. Porta J. Chem. SOC. Chem. Cornmun. 1993 1510. 41 D.A. Rockcliffe and A. E. Martell Inorq. Chem. 1993 32 3143. 42 D.A. Dixon N. P. Sadler and T. P. Dasgupta J. Chem.SOC.,Dalton Trans. 1993 3489. 43 S. M. Godfrey H. P. Lane A. G. Mackie C.A. McAuliffe and R.G. Pritchard J. Chem. SOC.,Chem. Commun. 1993 1190. 44 C. Taliani G. Ruani R. Zamboni R. Ilanieli S. Rossini V. N. Denisov V. M. Burlakov F. Negri G. Orlandi and F. Zerbetto J. Chem. SOC Chem. Commun. 1993 220. 45 R. Steudel K. Bergmann J. Buschmanii and P. Luger Angew. Chem. Int. Ed. Engl. 1993,32 1702. J.D. Woollins & C" "3 w"5 cu' ___c CN Figure 5 Formation of a macrocyclic binuclear copper complex during oxidation catalysis4' S,CI + Hg(SCN) -+ NCS,CN + HgCI (31 for the structures of H,S and S,Cl species. The oxidation of S'" by manganese(rI1) was studied.46 The structure and properties of SMe and SeMe were predicted on the basis of MO calculation^.^^ The reactions of FSO,N=SF were in~estigated;~~ for example treatment with C1F gives ClN(SO,F)(SF,) which adds to ethylene to form CICH,CH,N(SO,F)(SF,).A review on the formation of thioketones and thio- aldehydes included mention of some inorganic reagent^.^' A study of the accelerated sulfur vulcanization of alkenes" suggested that one of the possible active intermediates consists of the alkene bound by sulfur to the accelerator fragment. The use of B,S (formed in situ) for the formation of C,F,-CS-R species from the corresponding carbonyls has been described.'l The parent thioaldehyde C,F,CHS was formed and trapped with anthracene as a Diels-Alder adduct. The reactions of unsaturated nickel-tungsten and nickel-molydenum complexes such as (C,Me,)Ni-W(CO),(C,H,Me) with sulfur ligands such as diphenyl sulfide revealed oxidative 46 S.Mukhopadhyay and R. Banerjee J. Chem. SOC. Dalton Trans. 1993 933. 47 J.E. Fowler T.P.Hamilton and H.F. Schaefer 111 J. Am. Chem. Soc. 1993,115,4155. 48 T.Meier and R. Mews Chem. Ber. 1993,126 2431. 49 W.M. McGregor and D.C. Sherrington Chem. SOC.Rev. 1993 199. 50 P.Versloot M.van Duin J.G. Haasnoot J. Reedijk and A. L. Spek,J. Chem. SOC.,Chem. Commun. 1993 183. 51 J. Hasserodt H. Pritzkow and W. Sundermeyer Chem. Ber. 1993,126 1701. 0,S Se and Te addition across the mixed-metal bond to give (C,Me,)Ni(p-CO)(p-ER)W(CO)(ER)(C,H4Me).52A total synthesis of benzopentathiapin varacinium triflu~roacetate,~was reported; the penultimate stage of the reaction sequence (Equation 4) used S,C1 for direct removal of the ortho ester and formation of the pentathiapin moiety.If generally applicable this method could prove to be an interesting reaction for the preparation of a range of compounds containing S moieties. R = NH2 la R = NH2 TFA lb Reagents (i) TBAF THF 93% (ii) phthalimide DEAD PPh3 MF; (iii) hydrazine EtOH; (iv) (BoC)20 DMAP CH&; (v) S2C12 MF MeOH HCI A number of new P-S and As-S compounds were described. For example a-P4S3(H)R hydrides were obtaineds4 (and studied by NMR) in solution from a-P4S31,. Reaction of (C,Me,Et)Co(CO) with As4S4gave a mixture of compounds as shown in Equation 5.550P4S3 also undergoes cage-opening reactions; thus reactionssb of [{CpCr(CO),},] and P4S3 gave amongst other products [Cp4Cr4(CO),(P4S3)] in which a P4S ring bridges four [CpCr(CO),] fragments.Metal complexes with sulfur containing and sulfide ligands continue to be of interest. The thermal reaction of [Ru,(CO),,] with thioureas SC(NHR) (R = Et or Ph) gives larger clusters dependent on the R group. With R = ethyl a hexametal-containing cluster with a Ru boat is obtained whilst with R = phenyl a Ru cluster with a 'sofa' 52 A. F. Bartlone M. J. Chetcuti P. E. Fanwick and K. J. Haller Inorg. Chem. 1993 32 1435. 53 V. Behar and S.J. Danishefsky J. Am. Chem. SOC. 1993 115 7017. 54 B. W. Tattershall and N. L. Kendall J. Chem. SOC.,Dalton Trans. 1993 3163. 55 (a)H. Brunner B. Nuber L. Poll and J. Wachter Angew. Chem. Int. Ed. Engl. 1993,32 1627; (h)L.Y.Goh W. Chen and R.C. S.Wong Angew. Chem. Int. Ed. Engl. 1993 32 1728. J. D.Woollins conformation is formed.56 Hydrothermal syntheses of [Pt,S2,l4- and Pt(S4),12 were reported.57 The tetraplatinum compound contains a cubane like [Pt,S,I4+ core t with six Si -species bridging between platinium centres whilst the mononuclear complex has the expected square planar geometry about platinum with non-planar PtS rings. Perhaps the most structurally breathtaking compound of the year was [Cul,6~e7,(PPh,),o] prepared according58 to Equation 6. 146CuC1 + 73Se(SiMe,) + 30PPh3 + [Cu,,,Se,,(PPh,),,] + 146Me3SiC1 (6) The compound crystallizes in P6,lrnmc although not all of the carbon atoms could be located. The structure is shown in Figure 6.The PPh ligands which are bound to the 30 peripheral copper atoms shield the Cu,,,Se, core almost perfectly; the selenium atoms are arranged in planar layers with 21 31 and 21 atoms in an ABA arrangement. Smaller metal-sulfide clusters have also been studied. A novel solid M,Ag6S (M = Na K) was obtained from supercritical eth~lenediamine;~~ in the solid state the framework is built up of ocathedra of silver atoms with face bridging S atoms. A theoretical study6’ investigated the difference in reactivity with hydrogen and unsaturated molecules for (CpMo),(p-S),S,CH and [(CpMo),(p-S),(S,FeCp)]’; the former compound has an extensive chemistry at the disulfide ligand whilst the cationic species is not reactive. A [Fe8S6]4+ cluster was prepared by the reaction of [Fe6S6],[ (PMePh ),I with [RuI ,(MeCN),] .The compound [Fe,S6] -[Ru(SPMePh,)(MeCN),] contains the [Fe8S6I4+ cation with a cubic array of iron atoms and face bridging sulfur atoms; two of the face bridging sulfur atoms (on opposite sides of the cube) are also coordinated by one of the ruthenium atoms in the anions6’ A vanadium-sulfur cluster (NEt,),[V,O,S,(edt),].EtCN (edt = ethane-56 U. Bodensieck L. Hoferkamp H. Stoeckli-Evans and G. Suss-Fink J. Chem. Soc. Dalton Trans. 1993 127. ’’ K.-W. Kim and M.G. Kanatzidis Inorg. Chem. 1993 32 4161. ’*H. Krautscheid D. Fenske G. Baum and M. Semmelmann Angew. Chem. Int. Ed. Engl. 1993,32 1303. ’9 P.T. Wood W.T. Pennington and J. W. Kolis J. Chem. Soc. Chem. Commun. 1993 235. 6o D. L. DuBois F.Kvietok and M. R. DuBois Inorg. Chem. 1993 32 561. 61 S. Pohl W. Barklage W. Saak and U. Optiz J. Chem. Soc. Chem. Commun. 1993 1251. 0,S Se and Te 0=cu @=Se @‘P 4 Figure 6 The X-ray structure c~fCu,,,Se,,(PPh,)~~~~ 1,2-dithiol) with exu-[V0l2+ was reported as a model for the absorption of naked [VO]” units on vanadium sulfide surfaces. The result is of relevance in industrial hydrodesulfurization. Sulfinyl groups were studied in a number of systems. Thus flash vacuum pyrolysis of a-alkanesulfinyl phosphorus ylides results mainly in extrusion of Ph,P and the formation of thioesters; the proposed mechanism assumes the formation of sulfinylcar- bene intermediate^.^^ Related to this work was the report on the formation of a sulfinyl substituted tricarbonyl (arene)chromium(o) complex.64 The reactions of molybdenum and tungsten carbyne complexes to form q2 thiocarbene and q3 dithiomethyl complexes were also described.65 Furthermore methylene addition to coordinated SO gave the sulfene complex [Cp(dppm)Ru(CHR=S0,][PF6] which behaves as a K.A.York K. Folting and G. Christou J. Chem. Soc. Chem. Commun. 1993 1563. 63 R. A. Aitken M. J. Drysdale and B.M. Ryan J. Chem. Soc. Chem. Commun. 1993 1699. 64 A. Perez-Encabo S. Perrio A. M.Z. Slawin S. E. Thomas A. T. Wierzchleyski and D. J. Williams J. Chem. Soc. Chem. Commun. 1993 1059. 65 F. R.Kreissl W. Schutt C. M. Stegmair N. Ulrich H. Keller J. Ostermeier and E. Hertweck Chem. Ber. 1993 126 1609. 76 J. D.Woollins powerful carbon electrophile.The regioselectivity of the reaction for R = H with enamines isthe opposite of that observed for the free sulfene i.e.,coordination induces umpolung.66 A tungsten catalyst capable of inducing olefin metathesis and co-metathesis with sulfur-containing olefins was reported;67 although turnover rates were not as high as for non-substituted olefins the reactions were highly selective. Coordination chemistry of other sulfur rich species also provided some fascinating new systems. For example compounds of the type [M(C,S5),l2- (M = W Mo) were prepared and subsequently oxidized with a range of materials68 to give systems with electrical conductivities of up to 1O-'S cm-l. The reaction6' of PhNCO with MoO,(edtc) gave [Mo(NPh)(S,)(edtc),] (edtc = ethyldithiocarbamate) as a result of 0x0-substitution and double S-C cleavage of the thiocarbamate illustrating how difficult apparently straightforward reactions can become.An interesting CS insertion was observed for [(pp3)RhSMe] [pp = tris(2-(diphenylphosphino)-ethyl)phosphine] which yielded [(pp,)RhSC(S)SMe] .70 A series of aminesulfoxidedichloroplatinum(r1) complexes which were designed to bind to GpA sequences in DNA were prepared and ~haracterized~l and a new aqueous soluble thioporphyrin was reported.72 The usefulness of amides and sulfonamides as efficient locking-fragments in the template synthesis of macrocycles was ill~strated.~ A new aliphatic thiolato/thioether ligand provided a square planar environment for nickel to give a carbon monoxide dehydrogenease model that binds C0.74 The large cavity thioether in Equation 7 was prepared and coordinated to Co*"; the resulting redox chemistry at cobalt was significantly different to that previously reported for smaller homol~gues.~ An elegant one-pot synthesis (Equation 8)of a 22-membered thiocrown macrocycle by a 2 + 2 cycloaddition shows that there is still substantial work to be performed in this area.76 Metal complexes of thio (and seleno) macrocycles were also of interest.For example 2,l l-dithia/selena[3,3] orthocyclophanes were complexed with ruthe-ni~m;~~ the substituted cyclophane ligand adopts a rigid anti-I1 conformation. The development of main group compounds continues to be influenced by the availability of good reagents and in this regard silyl-species are especially important.A number of useful species were prepared. (Me,Si),CSeX (X = C1 Br I CN SCN) as well as [{(Me,Si),Se},E,] (E = S,Se) were obtained78 from [{(Me,Si),Se),]. The first tellurium-containing borazine derivative MeN[PhBN(Me)],TeCl, was obtained from [MeN{ PhBN(Me)SiMe,} ,]and TeCl whilst the spirocyclic [PhB(Bu'N),],Te was prepared from PhB(Bu'NLi) and TeCl,; the six-membered heterocycle is 66 W.A. Schenk P. Urban and E. Dombrowski Chem. Ber. 1993 126 679. 67 J.-L. Couturier K. Tanaka M. Leconte J.-M. Basset and J f.lllivier Angew. Chem. Int. Ed. Engl. 1993,32 112. 68 G.-E. Matsubayashi K. Douki H. Tamura M. Nakano and W. Mori Znorg. Chem. 1993 32 5990. 69 T. A. Coffey G. D. Forster and G. Hogarth J.Chem. Soc. Chem. Commun. 1993 1524. 70 M. di Vaira D. Rovai and P. Stoppioni Polyhedron 1993 12 13. 71 E.C. H. Ling G. W. Allen and T. W. Hambley J. Chem. SOC.,Dalton Trans. 1993 3705. 72 R. P. Pandian and T. K. Chandrashekar J. Chem. SOC.,Dalton Trans. 1993 119. 73 A. De Blas G. De Santis L. Fabbrizzi M. Licchelli A. M. M. Lanfredi P. Morosini P. Pallavicini and F. Ugouoli J. Chem. SOC.,Dalton Trans. 1993 1411. 74 T. Yamaura S. Sakurai H. Arai and H. Miyamae J. Chem. SOC. Chem. Commun. 1993 1656. 75 P. Osvath and A.M. Sargeson J. Chem. SOC.,Chem. Commun. 1993 40. 76 J. J. H. Edema H. T. Stock J. Buter R. M. Kellogg W. J. J. Smeets A. L. Spek and F. van Bolhuis Angew. Chem. Int. Ed. Engl. 1993 32 436. 71 L. R.Hanton and T. Kemmit Inorg. Chem.1993 32 3648. 78 M. Ostrowski I. Wagner W.-W. du Mont P. G.Jones and J. Jeske Z. Anorg. Allg. Chem. 1993,619,1693. 0,S Se and Te Me Me I 3On HO SH (iii) 1 Me Me I + I Me Reagents (i) (a) NaOEt EtOH; (b) HCI EtOH; (ii) LiAIH4 THF; (iii) SOC12 CHCI,; (iv) Cs,CO, dimethylforrnamide,60 "C 34h (OBs = benzene sulfonate) CsHTHF,MeOH.NaOMe A ~ CSH B(OP& A/(OPr')3 t Is 3 K X (2a-c) a; X=HP Y = Br bX=O Y=U C; X = CH2 Y = CI distorted from planar with the TeCl group being out of the plane of the other ring atoms.79 Organo-B-S-N heterocycles were also described.*' The first stable 1,2-thia/selenastannetes were reported from the thermal decomposition of sterically crowded precursors.* The reactions of sulfur and selenium with primary phosphines 79 H.-J.Koch H. W. Roesky S. Besser and R. Herbst-Irmer Chem. Ber. 1993 126 571. *' B. Wrackmeyer K. Wagner and R. Boese Chem. Ber. 1993 126 595. N. Tokitoh Y. Matsuhashi and R. Okazaki J. Chem. Soc. Chem. Commwn. 1993 407 J. D.Woollins were studied. As expected compounds of the type RP(E)H are formed;82 in the presence of ketones the (l-hydroxyalkyl)-organyl-phosphine-sulfide/selenidesare formed cleanly. Amongst the binary compounds of interest was the report of the preparation of tin- and lead-chalcogenides via solid state metathesis reactions8 as were studies into the P-Se binary system at high temperature^.^^ A number of selenium-containing complexes were described. For example [Se'VS~Mo603]8-was obtained from aqueous solution; the anion has a pyramidal SeS group in its centre and a ring of six MOO octahedra linked by corners and edges.85 Several novel triselenidotantalum half-sandwich complexes were reported.86 Systems containing naked anions continue to be extensively studied; [MO~Q~(S~),(S~,),]~-0 Se) was prepared and characterized.The binuclear (Q = compound contains three different types of coordinated selenium atoms.87 A stable selenodiimide complex (BuN),SeSnC14.2thf was crystallized the diimide coordinates through two N atoms whilst the two thf molecules complete approximate tetrahedral coordination about the selenium.88 The first example of a selenium macrocycle coordination complex was reported.89 The X-ray structure (Figure 7) reveals the rhodium complex to have similar geometry to the analogous sulfur compound.Figure 7 The X-ray structure of trans-[RhCl,([ 16]aneSe,)] Studies on simple selenium and tellurium systems have also been reported. Thus 77Se and 125Te NMR spectroscopy on S/Se/Te melts were conducted.90 The use of E2-82 F. Uhlig E. Herrmann D. Schaidler G. Ohms G. Grossmann S. Besser and R. Herbst-Irmer Z. Anorg. Allg. Chem. 1993 619 1962. 83 I. P. Parkin and A. T. Rowley Polyhedron 1993 32 2961. 84 R. Maxwell and H. Eckert J. Am. Chem. Soc. 1993 115,4747. 85 C. Robi and K. Haake J. Chem. SOC.,Chem. Commun. 1993 397. 86 K. Tatsumi H. Kawaguchi and K. Tani Angew. Chem. Int. Ed. Engl. 1993 32 591. 87 B. W. Eichorn D. R. Gardner A. Nichols-Ziebarth K.J. Ahmed and S. G. Bott Inorg. Chem. 1993,32 5412. 88 J. Gindl M. Bjorgvinsson H. W. Roesky C. Freire-Erdbrugger and G. M. Sheldrick,J. Chem.Soc. Dalton Trans. 1993 81 1. 89 P. F. Kelly W. Levason G. Reid and D. J. Williams J. Chem. Soc. Chem. Commun. 1993 1716. 90 T. Chivers R. S. Laitinen K. J. Schmidt and J. Taavitsainen Inorg. Chem. 1993 32 337. 0,S Se and Te (E = Se Te) for the conversion of cis-uicinal diols into olefins was described.” A stable telluroketone was prepared9 by thermal decomposition of a 1,3,4-tellurdiazoline according to Equation 9. A rather more reactive telluroketone was also ~btained.’~ Pyrolysis of Me,SnTeCF at 280” gave TeCF in good yield. Unlike the telluroketone shown in Equation 9 TeCF is thermally unstable and rapidly dimerizes on warming.The X-ray structures of (C,F,),TeX (X = C1 Br) were reported.’ A number of dithiocarbamate complexes of tellurium were also described.” Interesting- ly the geometry about tellurium in Me,Te(S,CNMe,) appears to be similar to that in (C,F,),TeX ;the dithiocarbamate ligands coordinate the tellurium in a monodenate fashion. A tellurium-containing molybdate was prepared and characterized.’ An overview of tellurium transition metal chemistry was given.97 Some new tellurium-containing chalcogenide-cubane-containingdivalent transition metal ions were rep~rted.’~ [(Cp*AlE),] (Cp* = Me,C,; E = Se Te) was also prepared and shown to have a cubane type str~cture.’~ Although slightly outside of the scope of this review the preparation’” of layered ternary MGeTe (M = Ti Zr Hf) indicates the current interest in solids containing heavier chalcogenides.Another interesting solid state material is Ta,Pd,Te which contains palladium in a distorted tetrahedral environ- ment.’” Finally in this section it is worth noting the synthesislo2 of the new Sb-Te zintl anions [Sb,Te,14- and [sb,Te6l3-. Chalcogen-nitride chemistry continues to provide many interesting new com-pounds. Organo-S-N compounds are being studied by a number of groups. Highlights include the preparation’ O3 of chlorthiatriazine [(ClCN)(ClSN),] from (NSCl) and ClCN; [(ClCN),(ClSN)] and (ClCN) were also obtained. Aryl 1,5-dithia-2,4,6,8- tetrazocines were reinvestigated. ’O4 Free radical organo-S-N rings and related systems 91 D.L.J. Clive and P. L. Wickens J. Chem. SOC.,Chem. Commwn. 1993 923. 92 M. Minoura T. Kawashima and R. Okazaki J. Am. Chem. SOC.,1993 115 7019. 93 R. Boese A. Haas and C. Limberg J. Chem. SOC.,Dalton Trans. 1993 2547. 94 D. Naurnann L. Ehmanns K.-F. Tebhe and W. Crump Z. Anorg. Allg. Chem. 1993,619 1269. 95 J.H. E. Bailey and J. E. Drake Can. J. Chem. 1993 71 42. 96 C. Rob1 and M. Frost Z. Anorg. Allg. Chem. 1993 619 1624. 97 U. Sierneling Angew. Chem. Int. Ed. Engl. 1993 32 67. 98 H.-0. Stephan C. Chen G. Henkel K. Griesar and W. Haase J. Chem.Soc. Chem. Commun. 1993,886. 99 S. Schulz H. W. Roesky H.-J. Koch G.M. Sheldrick,D. Stalke and A. Kuhn Angew. Chem. Int. Ed. EngI. 1993 32 1729. loo A. Mar and J. A. Ibers J. Am. Chem. SOC.,1993 115 3227.W. Trernel Angew. Chem. In?. Ed. Enyl. 1993 32 1752. lo’ C. J. Warren D. M. Ho R. C. Haushalter and A.B. Bocarsly Angew. Chem.,In?. Ed. Engl. 1993,32 1646. ‘03 S.-J. Chen U. Behrens E. Fischer R. Mews F. Pauer G. M. Sheldrick D. Stalke and W.-D. Stohrer Chem. Ber. 1993 126 2601. Io4 R. T. Boere K.H. Moock S. Derrick W. Hoogerduk K. Preuss J. Yip and M. Parvez Can. J. Chem. 1993 71 473. J. D. Woollins also attracted attention.' 05-'07 A substantial paper summarized much chemistry of iminoaminosulfinates.'08 Binary Se-N systems were also studied. The reactivity of Se,N in liquid ammonia was de~cribed."~A number of Se-N cations were prepared.' ' O-' ' A new fluorinated S-Se-Te-N cation was prepared' ' according to Equation 10.A slightly improved preparation of Se,N was reported." An old problem was revisited when ab initio calculations were used to rationalize the geometries of the cyclic (RSeN) and (R,PN) systems;"' the tub conformation is preferred since it maximizes d orbital usage although this conclusion is hardly new! Mechanistic studies on reaction of selenic anhydrides were also reported.' ' (1) >95% (2)>95% Metal complexes of S-N ligands were also studied. The preparation and X-ray structure of fac-[PtBr,(S,N,)] -revealed the structure predicted from NMR studies.' l7 Hydrolysis of [Pt(NSO),(PMe,Ph),] gave [(PMe,Ph),Pt-(SO,),Pt(PMe,Ph),] which contains a six-membered chair Pt,S,O ring.' '' P-S/Se-N systems were also studied. The unusual seven-membered diaza-phospha- tetrathia heterocycle was obtained' l9 according to Equation 11.Some coordination chemistry of [Ph,PN(Ph)P(E)Ph,] (E = S Se) was described.I2' Finally in continu- ations of work mentioned in last years report a lithium salt and further platinum complexes of P-S/Se-N cages were described. ' ' 3 ' lo' P.D. Boyle S. Parsons J. Passmore and D. J. Wood J. Chem. Soc. Chem. Commun. 1993 199. Io6 A. J. Banister I. Lavender J. M. Rawson W. Clegg B. K. Tanner and R. J. Whitehead J. Chem. SOC. Dalton Trans. 1993 1421. lo' S. Parsons J. Passmore and P. S. White J. Chem. SOC.,Dalton Trans. 1993 1499. lo' S. Freitag W. Kolodziejski F. Pauer and D. Stalke J. Chem. SOC.,Dalton Trans. 1993 3479. log P.F. Kelly and J.D. Woollins Polyhedron 1993 12 1129. (a)E.G.Awere W. V. F. Brooks J. Passmore P.S. White X. Sun and T.S. Cameron J. Chem. SOC. Dalton Trans. 1993,2439; (b)E. G.Awere J. Passmore and P. S. White J. Chem.SOC.,Dalton Trans. 1993 299. M. Broschag T. M. Klapotke and A. Schulz Inorg. Chem. 1993 32 5734. J. Silvari T. Chivers and R. S. Laitinen Inorg. Chem. 1993 32 4391. A. Haas and M. Pryka J. Chem. SOC.,Chem. Commun. 1993,993. '14 J. Silvari T. Chivers and R. S. Laitinen Inorg. Chem. 1993 32 1519. 'I5 D. H. R. Barton M. B. Hall Z. Lin and S.I. Parekh J. Am. Chem. SOC. 1993 115 955. '16 D.H.R. Barton and S.I. Parekh J. Am. Chem. SOC. 1993 115 948. '" V.C. Ginn P. F. Kelly A.M. Z. Slawin D. J. Williams and J. D. Woollins Polyhedron 1993 12 1135. 'I' V.C. Ginn P. F. Kelly C. Papadimitriou A. M. Z.Slawin D. J. Williams and J. D. Woollins J. Chem. SOC. Dalton Trans. 1993 1805. 'I9 S.E. Bottle R.C. Bott I. D. Jenkins C. H. L. Kennard G. Smith and A. P. Wells J. Chem. Soc. Chem. Commun. 1993 1684. M. S. Balakrishna,'R. Klein S. Uhlenbrock A. A. Pinkerton and R. G. Cavell Inorg. Chem. 1993 32 5676. T. Chivers M. Edwards R. W. Hilts M. Parvez and R. Vollmerhaus,J. Chem.SOC.,Chem. Commun. 1993 1483. ''' T. Chivers D. D. Doxsee R. W. Hilts and M. Parvez Can. J. Chem. 1993 71 1821. 0,S Se and Te (1)a; R= But b;R=Ph 1 ? Ph Ryp:yA s\rs s-s (3)a; R = Bu' b; R = Ph

ISSN:0260-1818    

DOI:10.1039/IC9939000067

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

7 The Halogens and Noble Gases By D.A. ARMITAGE Department of Chemistry King's College London Strand London WCZR ZLS UK 1 Introduction This chapter covers the 1993 literature and follows last years format. 2 Polyhalide Ions and Dihalogen Adducts [K(Crypt-2.2.2)],I1 results from the reaction of [K(Crypt-2.2.21'1-with iodine in ethanol/methylene chloride. The anion possesses Ci symmetry with two V-shaped penta-iodide groups bridged through their vertices by an I molecule.' 1,4,7-Trithiacyclononane forms 1:1 and 1 :2 charge-transfer complexes the latter showing a polymeric structure with I bridging the thioether units. The imidazol-2-ylidene (1) forms a stable adduct with iodine in which the C-I bond is 210.4 pm and the 1-1 bond 334.8 pm with the C -I -I unit almost linear (Equation 1).3 (11 The changes in the Raman spectra of aqueous solutions of I in HI (1 :1mole ratio) with changing concentration reflect the presence of the ion pair H'I; ,which gives a stretching band at 172 cm- due to the strong 1-1 bond.The spectrum of Br in HBr may be similarly interpreted but other bromine species are also pre~ent.~ Ph3P reacts with CH,I in CH,Cl to give the ionic adduct Ph3PCH21fI- which exists in the solid state as two discrete monomer units with remarkably short iodine-iodine separations of 346.5 and 356.3 pm.' With bromine in CH,Cl, Ph3P gives light brown crystals of Ph,PBr+Br; which exist as discrete monomeric cations and anions. The Br-Br bonds are almost equal in the tribromide ions which are slightly bent.6 ' K.F.Tebbe and A. Kavoosian Z. Naturforsch. Teil B 1993 48 438. A. J. Blake R.O. Gould C. Radek and M. Schroder J. Chem. SOC. Chem. Commun. 1993 1191. ' N. Kuhn T. Kratz and G. Henkel J. Chem. SOC. Chem. Commun. 1993 1778. J. Milne Spectrochim. Acta A 1992 48 533. H. Vogt K. Lauritsen L. Riesel M. von Lowis and G. Reck Z. Naturforsch. Teil B 1993 48 1760. H. Vogt S.I. Trojanov and V. B. Rybakov 2.Naturforsch. Teil B 1993 48 258. 83 D. A. Armitage R,PIBr results from mixing ether solutions of the phosphine and IBr the phenyl derivative indicating a predominance of Ph,P-I-Br in the solid state though small quantities of Ph,P-Br-I were dete~ted.~ The ,'P-{H) NMR spectra for R,Pl adducts support an ionic structure in CDCl but the solid state 31P-{H} magic angle spinning NMR data indicate a molecular four-coordinate R,P-I-I structure.' Ph,AsI oxidizes Co,(CO) in a 6 1 molar ratio to produce [Ph,As-I-I-I-AsPh,] + [Ph,AsCoI,] -with a linear cation,' while R,PI and unactivated cobalt give the novel ionic complexes [R,PI] +[R,PCoI,]-.The latter type of complex is produced along with the cobalt(II1) derivative Co(R,P),I if R = PhMe,. Ph,PIBr reacts with cobalt to give [Ph,PI] +[Ph,PCoIBr,] - Ph,SbI behaves similarly giving [Ph,SbI] +[Ph,SbCoI,] -.lo 3 Cationic Iodine and Iodine Coupling Reactions (2,4,6-Me,C,H,N),I +PF has been shown to ring-close terminally unsaturated carboxylic acids that are gem-dimethylated to give iodomethyl substituted seven- to eleven-membered ring lactones (Equation 2).' ' Py21 BF has been found to regioselectively mono- and poly-substitute benzene at + room temperature.Good yields result for iodo p-diodo 1,2,4,5-tetra- penta- and hexa-iodobenzenes while the 1,2,4-derivative results regioselectively from p-di-iodo- benzene (Equation 3).' Py,I+BF also couples iodoalkynes to give the di-iodoeneyne (Equation 4).' R\ /I 2RCECI + Py*I* CW'2 C/C= c I (4) R ' N. Bricklebank S. M. Godfrey C. A. McAuliffe and R. G. Pritchard J. Chem. SOC.,Dalton Trans. 1993 2261. N. Bricklebank S. M. Godfrey A.G. Mackie C. A. McAuliffe R. G. Pritchard and P. J. Kobryn J. Chem. SOC.,Dalton Trans. 1993 101. S. M. Godfrey H. P. Lane A.G. Mackie C.A. McAuliffe and R.G. Pritchard J. Chem. SOC. Chem. Commun.1993 1190. lo S. M. Godfrey H. P. Lane C. A. McAuliffe and R.G. Pritchard J. Chem. SOC.,Dalton Trans. 1993 1599. B. Simonot and G. Rousseau Tetrahedron Lett. 1993 34 4527. l2 J. Barluenga J. M. Gonzalez M. A. Garcia-Martin and P.J. Campos Tetrahedron Lett. 1993,34 3893. l3 J. Barluenga J. M. Gonzalez I. Llorente and P. J. Campos Angew. Chem. Int. Ed. Engl. 1993,32 893. The Halogens and Noble Gases (Z)-[/3-(Phenylsulfonyl)alkenyl]iodoniumtetrafluoroborates have been found to react with PhS0,Na to give (Z)-l,2-bis(phenylsulfonyl)alkenes(Equation 5).14 Unsymmetrical perfluoroalkynes result from thermal coupling of R,'C=CH with R:I at 220 "C the intermediate alkene Rf CI = CHR; dehydro-iodinating under phase transfer catalysis using tetra-n-butylammonium bisulfate.l5 Irradiation couples C,F,I with anilines N-heterocycles phenyl ethers and phenols.16 271Mossbauer spectra of dimeric Ar(Ph)I halides show the valence electron population of iodine to depend on the C-I interaction and not the halogen.17 4 Organo-iodine Oxygen Compounds Iodosylbenzene diacetate oxidize phenols to quinones and to cyclohexa-23-dienones,18 while the bicyclic dienol (2) is oxidized to the tricycle (3) (Equation 6)." The trifluoroacetate analogue PhI(OCOCF,) oxidizes phenylhydrazones of a-keto esters to a-keto acids,,' and with Me,SiCN and Me,SiOTf gives the aryl(cy- ano)iodonium triflate (4) (Equation 7).21This substitutes a wide range of unsaturated organostannyl derivatives (for example Equation 8).22 ArI(OCOCF3)2 + Me3SiCN/Me3SiOTf -[ArICNr[OTfJ-(') l4 M.Ochiai K. Oshima Y. Masaki M. Kunishima and S. Tani Tetrahedron Lett. 1993 34 4829. V. Sanchez and J. Greiner Tetrahedron Lett. 1993 34 2931. l6 Q.-Y. Chen and Z.-T. Li J. Chem. SOC.,Perkin Trans. 1 1993 1705. " H. Ikezawa M.Takahashi M. Takeda and Y. Ito Bull. Chem. SOC.Jpn. 1993 66 1959. A. Pelter and S. M. A. Elgendy J. Chem. SOC.,Perkin Trans. 1 1993 1891. l9 C. E. Mowbray and G. Pattenden Tetrahedron Lett. 1993 34 127. D.H.R. Barton J.Cs. Jaszberenyi and T. Shinada Tetrahedron Lett. 1993 34 7191. '' V. V. Zhdankin M.C. Scheuller and P.J. Stang Tetrahedron Lett. 1993 34 6853. 22 R.J. Hinkle G.T. Poulter and P. J. Stang J. Am. Chem. SOC. 1993 115 11 626. D. A. Armitage The mono-alkynyl substituted bis-iodonium triflate of p-di-iodobenzene (5) cyclizes to benzofuran in the presence of phenoxide ion (Equation 9).23 Iodosylbenzene hydroxylates benzylsilanes at the a-position these a-hydroxysilanes hydrolyse to the ben~aldehyde.~~ Iodosonaphthoates and iodosopyridinium car-boxylates rapidly cleave p-nitrophenyldiphenylphosphonate providing decon-taminants for reactive toxic phosphate^.^' Sulfonamides react with PhI(OMe) to give arylsulfonylimino-iodobenzenes ArSO,=IPh which can be converted into the isocyanate using CO.and with a Pd" complex as a catalyst (Equation Pt11(0Me)~+ ArS02NH2 -ArS02NzIPh =ArSO2NCO + PhI (10) Pd" 5 Oxide Derivatives Calculations suggest that both the axial and equatorial I-F bonds in IOF (C4" symmetry) are the same length (182.6 pm) with an 1=0 bond length of 172.5 pm and an OIF bond angle of 97.2".27 Bromine reacts with ozone at -60°C to give orange crystals which were shown by analysis to contain Br,O,.The structure indicates the presence of bromine in both +1 and +5 oxidation state and is conveniently represented as Br'OBr'O,. The Br-0 multiple bonds are about 162 pm and the single ones 185pm. The oxide is dimeric (6) through a weak interaction between the bromine(1) atoms of 299.5 pm.28 B? 23 T. Kitamura L. Zheng H. Taniguchi M. Sakurai and R. Tanaka Tetrahedron Lett. 1993 34 4055. 24 E. Baciocchi and 0. Lanzalunga Tetrahedron 1993 49 7276. 25 R. A. Moss H. Zhang S. Chatterjee and K. Krogh-Jespersen Tetrahedron Lett. 1993,34,1729; R. A. Moss and H. Zhang ibid.1993 34 6225. 26 G. Besenyei S. Nemeth and L. I. Simandi Tetrahedron Lett. 1993,34,6105;G.Besenyi and L. I. Simandi ibid. 1993 34 2839. '' K.O. Christe E.C. Curtis and D.A. Dixon J. Am. Chem. SOC. 1993 115,9655. 28 R. Kuschel and K. Seppelt Angew. Chem. Int. Ed. Engl. 1993 32 1632. The Halogens and Noble Gases The kinetics of iodine hydrolysis have been further studied and a consistent set of rate and equilibrium constants presented.,’ 6 Azide Derivatives Bromine azide results from the reaction between Br and sodium azide. The molecular structure as determined by electron diffraction in the gas-phase indicates bromine bonding to the terminal nitrogen atom of the almost linear azido group and a tetrahedral BrNN bond angle (7). The N-N bond lengths are 123 and 113 pm and the N-Br bond is 190 pm.,’ Iodine azide (8) has been obtained from silver azide and found to be polymeric with the monomer unit having a similar structure to that of bromine azide.The I-N bonds are almost the same length.31 Y Y ‘I Y /I’ N ‘I /I 0 Y Y Y N N Reacting Me,SiN with ICll AsF gives the I(N,)l cation. Calculations indicate C symmetry as being most stable with I-N bonds of about 204pm some 22-26pm shorter than those of polymeric IN3., All these halogen azides are explosive. PhIO/Me,SiN rapidly and cleanly converts N,N-dimethylaminoarenes and py- ridines into the aminomethylene azide (Equation 1 l)., 7 Haloammonium and Sulfonium Salts CF,NCl has a ClNCl angle of 11 1 Soand can be fluorinated by XeF’ to give both CF3NC1,F+ and CF,=NClF+ .34 Sulfenium salts Cl,CSX+AsF; result from the reaction of Cl,C=S and X,/AsF (X = C1 Br) while MeSH and XeFLSbF; give MeS(H)F+SbF; which with Br forms the MeS(Br)F+ salt.35 Photolysing 29 I.Lengyel I. R. Epstein and K. Kustin Inorg. Chem. 1993 32 5880. ’O M. Hargittai I.C. Tornieporth-Oetting T. M. Klapotke M. Kolonits and I. Hargittai Angew. Chem. Int. Ed. Engl. 1993 32 759. 31 P. Buzek T. M. Klapotke P. von Rague Schleyer 1.C. Tornieporth-Oetting and P.S. White Angew. Chem. Int. Ed. Engl. 1993 32 275. 32 I.C. Tornieporth-Oetting T. M. Klapotke A. Schulz P. Buzek and P. von Rague Schleyer Inorg. Chem. 1993 32 5640. ’’ P. Magnus J. Lacour and W. Weber J. Am. Chem. SOC. 1993 115 9347. 34 R. Minkwitz D.Larnek M. Korn and H. Oberharnrner Z. Anorg. Allg. Chem. 1993 619 2066. 88 D.A. Armitage FC(0)SBr in a rare gas matrix gives SBrF calculations indicate S-F and S-Br bond lengths of about 1.6A and 2.1 A respectively and a bond angle of 101°.36 8 Noble Gases Structural studies on XeOF; SbF show the cation to have a disphenoid-shaped array with two axial Xe-F bonds longer than one of the equatorial Xe-F bonds but shorter than the two equatorial interactions with fluorine atoms of two adjacent SbF; anions.37 Calculations show that TeF; IF, and XeF; each have a pentagonal bipyramidal equilibrium geometry with stable XeF; adopting a monocapped trigonal prism as the transition state for axial-equatorial exchange.38 C,F,Xe +AsF reacts with PX to give isomeric mixtures of biphenyls XC,H,C,F (X = Me F CF, NO, CN).39 An unexpectedly stable covalent acyloxyxenon(r1) derivative results on reaction with a caesium pentafluorobenzoate in water (Equation 12).The crystal structure indicates a linear F,C,-Xe-0 arrangement with dimeriz- ation through Xe-0 bridging.40 Aryl boranes react with XeF to give ArXe' salts with arylfluoroborate anions. These salts vary in thermal stability with the 2,6-difluoroaryl species being more stable than monofluoroaryl derivati~es.,~ Aryl trimethylsilanes are readily fluorodesilylated with XeF to give the aryl fluorides while vinyl stannanes and XeF,/Ag triflate give fluoro alkene~.~ C,F,MX3 (M = Si Ge; X = C1 Br) undergoes halogen exchange with XeF without C-M cleavage however if X = F or alkyl XeF' yields the heptafluorocyclohexadienyl derivative C6F,MX3 .43 The first alkenylxenon(I1) deriva- tives result similarly with [C6FSXe]+[ASF6]- reacting with XeF in HF to give first the (heptafluoro- 1,4-cyclohexadien- l-yl)xenon(~~) derivative then the (nonafluoro- cyclohexen-1-yl)xenon(II)salt.44 Both are stable at room temperature (Equation 13).With di- tri- and tetra-phenylethene the vicinal difluorides result in high yield using XeF ,/H F.4 35 R. Minkwitz and W. Meckstroth Z. Anorg. Allg. Chem. 1993 619 583; R. Minkwitz and B. Back 2. NaturSorsch. Teil B 1993 48 694. 36 C.O. Della Vedova and H.-G. Mack Inorg. Chem. 1993 32,948. 37 H. P.A. Mercier J.C.P. Sanders G. J. Schrobilgen and S.S. Tsai Inorg. Chem. 1993 32,386.38 K.O. Christe D.A. Dixon J.C. P. Sanders G. J. Schrobilgen and W. W. Wilson,J. Am. Chem. SOC.,1993 115 9461. 39 H. J. Frohn A. Klose and V. V. Bardin J. Fluorine Chem. 1993 64 201. 40 H.J. Frohn A. Klose and G. Henkel Angew. Chern. Inr. Ed. Engl. 1993 32,99. 41 H. J. Frohn and Chr. Rossbach 2.Anorg. Allg. Chem. 1993,619,1672; D. Naumann H. Butler R. Gnann and W. Tyrra Inorg. Chem. 1993 32 861. 42 A. P. Lothian and C.A. Ramsden Synlett 1993,753;M. A. Tius and J. K. Kawakami Synlett 1993,207. 43 V.V. Bardin and H. J. Frohn J. Fluorine Chem. 1993 60,141. 44 H. J. Frohn and V. V. Bardin J. Chern. SOC.,Chem. Commun. 1993 1072. 45 M. Zupan M. Metelko and S. Stavber J. Chem. SOC.,Perkin Trans. 1 1993 2851. The Halogens and Noble Gases 89 Substituted benzyl alcohols undergo rearrangements on fluorination with XeF to give the fluoromethyl aryl ether.46 Fluorodecarboxylation of carboxylic acids with XeF involves a free radical mechanism while the perfluorodicarboxylic acid HO,C(CF,),CO,H in the presence of arenes gives Ar(CF,),Ar.47 It also fluorinates five-coordinate carbonyl complexes of Ir' to yield the fluoroacyl derivative with Ir(CO),(PEt,)l giving Ir(CO),F(COF)(PEt,),.48 129Xe NMR studies of Xe gas in porous silica gels show the NMR absorption to be pore size dependent.Since zeolites contain strongly acidic sites it is also found that the '29Xe spectra are strongly affected by acidic solvents.49 Reacting Xei with bromide or iodide in the presence of Xe provides a route to the excited complex (exciplex) XeBr* and XeI*.'O CHCl and CH,Cl undergo both H and C1 exchange with fluorine by using XeF,.'l The molecular dynamics of XeF,L in MeCN HF and BrF have been studied., 9 Hydrogen Fluoride Traps Pyridinium poly(hydrogen fluoride) (PPHF) readily fluorinates a range of chloro and amino-silanes to give the hexafluorosilicate with the Si-C1 Si-H and Si-N bonds all being cleaved at room temperature.' Poly-4-vinylpyridinium poly(hydrogen fluoride) (PVPHF) provides a convenient solid state fluorinating agent with up to 60% HF.It readily hydrofluorinates alkenes and alkynes and fluorinates alcohols. With N-bromosuccinimide and PVPHF bromofluorination of alkenes result^.'^ The proton sponge hydrofluoride [l ,8-(Me,N),CloH,-HF] is soluble in acetonitrile and fluor- inates the C-CI bonds of 2,4,6-trichloropyridine and benzoyl chloride.,' 10 Chlorofluorocarbons There appears to be a recent decrease in the growth rates of the atmospheric concentration of the chlorofluorocarbons CFC-11 (CFC1,) and CFC- 12 (CF,Cl,).This is based on measurements spanning the last 15 years and covers latitudes from 83 ON to 90"s. The results are consistent with the estimates of CFC-producers of reduced emission^.,^ Chromium(rI1) oxide prepared by dehydrating the hydroxide at between 350 "C and 450 "C catalyses the substitution of chlorine in CF,CH,Cl using HF. The activity is proportional to the number of chromium atoms that are reversibly oxidized.57 46 S. Stavber and M. Zupan Tetrahedron Lett. 1993 34 4355.47 T. B. Patrick S. Khazaeli S. Nadji K. Hering-Smith and D. Reif J. Org. Chem. 1993,58,705; V. K. Brel V. I. Uvarov N. S. Zefirov P. J. Stang. and R. Caple J. Org. Chem. 1993 58 6922. 48 E.A. V. Ebsworth N. Robertson and L.J. Yellowlees J. Chem. Soc. Dalton Trans. 1993 1031. 49 V. V. Terskikh 1. L. Mudrakovskii and V. M. Mastikhin J. Chern. Soc. Faraday Trans. I 1993,89,4239; E. M. Arnett and P.C. Wernett. J. Am Chem. Soc. 1993 115 12 187. 50 S.P. Mezyk R. Cooper and J. Sherwell J. Phys. Chem. 1993 97 9413. 5' W. W. Dukat J.H. Holloway E. G. Hope P. J. Townson and R. L. Powell J. Fluorine Chem.. 1993 62 293. 52 Sh.Sh. Naniev and 1.1. Ostroukhova Spectrochirn. Acta A 1993 1527 and 1537. 53 K. N. Radhamani and D. K. Padma J Fluorine Chem.. 1993 64 95.s4 G.A. Olah X.-Y. Li Q. Wang and G K.S. Prakash Synthesis 1993 693. 5s R.D. Chambers T. F. Holmes S. R. Korn and G. Sandford J. Chem. Soc. Chem. Commun. 1993 855. " J. W. Elkins T. M. Thompson T. H. Swanson J.H. Butler. B. D. Hall S.O. Cummings D. A. Fisher and A.G. Raffo Nature 1993 364,780. 57 J. Barrault S. Brunet B. Requieme and M. Blanchard J. Chem. Soc. Chem. Commun. 1993. 374. D.A. Armitage 11 Miscellaneous The reaction of F2+ with benzene in the gas-phase proceeds by way of single electron-transfer to give C,Hi .58 Weak intermolecular c1- -N interactions between 2,3-dicyano-5,6-dichlorobenzenesallow the design of linear molecular tapes.59 Reacting (Me,C,),ZrMe with [(C,F,),BOH]- gives (Me,C,),ZrOB(C,F,) the structure of which shows one of the C6F5 groups to form a C-F-Zr bridge with one of the ortho fluorine atoms of the ring.,' S.T.Purrington C.A. Haney and R. D. Voyksner J. Fluorine Chem. 1993 65 97. 59 D. S. Reddy K. Panneerselvam T. Pilati and G.R. Desiraju J. Chem. SOC. Chem. Commun. 1993 661. 6o A. R. Seidle R.A. Newmark W. M. Larnanna and J. C. Huffman Organornefal[ics 1993 12 1491.

ISSN:0260-1818    

DOI:10.1039/IC9939000083

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

8 Zn,Cd and Hg By H. SLOAN Consulting Chemist 40 Wendan Road Newbury Berkshire RG 14 7AF UK 1 Introduction Reviews have appeared on tellurometalates of zinc (and copper),' the electronic structure of active sites on copper/zinc oxide catalysts for methanol synthesis,2 polyfunctional organozinc reagents in organic synthesis, biological functions and coordination motifs of zinc intramolecular equilibria in binary complexes (zinc and copper) of gly~inates,~ Schiff base and tetra-coordinated chelates of zinc (in part),6 and mercury as a structural building block in metal-metal bonded system^.^ The chemistry of the copper and zinc triads are the subject of a special report.' Difficulties in the calculation and interpretation of '',Cd chemical shifts from NMR data have been discussed.' 2 Metal-Metal Bonds A theoretical study of HgX HgX, and Hg,X (X = H F,C1 Me CF,) has indicated" the influence of the electronegativity of X on the stability of the Hg-Hg bond.The reaction of CdCl with KBH in Et,O at -78 "C followed by TlTp' gave" compound (1).An X-ray structural determination indicated an q2 coordination of the borohydride ligand and this was confirmed by IR spectroscopy. The mass spectrum of (1) contains a cluster of peaks corresponding to (2) and (2) was synthesized by the reaction of CdC1 and LiBHEt followed by TlTp'. The 'H NMR spectrum of (2) is normal for the Tp' ligand with no other resonances present. The ",Cd NMR spectrum shows a large central resonance with satellites due to '''Cd with appropriate relative intensities.The '''Cd-' ',Cd coupling constant is very large (20646 Hz) indicating a strong Cd-Cd bond. M.A. Ansari J. M. McConachie and J.A. Ibers Acc. Chem. Res. 1993 26 574. E.I. Solomon P. M. Jones and J. A. May Chem. Rev. 1993 93 2623. P. Knochel and R. D. Singer Chem. Rev. 1993 93 2117. B.L. Vallee and D. S. Auld Angew. Chem. Int. Ed. Engl. 1993 32 543. ' H. Sigel Coord. Chem. Rev. 1993 122 227. A. D. Garnovskii A.L. Nivorozhkin and V.I. Minkin Coord. Chem. Rev. 1993 126 1. ' L.H. Gade Angew. Chem. Int. Ed. Engl. 1993 32 24. The Chemistry of the Copper and Zinc Triads ed. A. J. Welch and S. K. Chapman The Royal Society of Chemistry Cambridge 1993. P. D. Ellis J. D. Odom A. S. Lipton and J. M. Gulick J. Am. Chem. SOC.1993 115 755. lo P. Schwerdtfeger P. D. W. Boyd S. Brienne J. S. McFeaters M. Dolg M.-S. Liao and W. H. E. Schwarz Znorg. Chim. Acta 1993 213 233. D. L. Reger S.S. Mason and A. L. Rheingold J. Am. Chem. Soc. 1993 115 10406. 91 92 H. Sloan (1) &?N% = Tp’) 3 Carbon-donor Ligands The reaction of MeHgCl with NaBX (X = H D) in alkaline aqueous solution gavel2 MeHgX species which were identified from mass spectroscopic and NMR evidence. Exposure of suspensions of KCd[Fe(CN),] to ultrasound has been shown13 to cause linkage isomerization in that Fe-CN-Cd linkages are converted into Fe-NC-Cd linkages. This effect occurs at lower temperatures than those previously known for thermal linkage isomerization. Addition of warm aqueous [PPh,]Br to a solution of cadmium chloride and K,[Cd(CN),] gave‘ a precipitate which was recrystallized as [PPh,] ,[Cd,(CN),] from a mixture of citric acid 2-aminoethanol and acetonitrile with the pH being kept in the range 7.7-8.3.Structural determination showed that the anion has a disordered bridging cyanide ligand (3) with the Cd-C-N-Cd moiety being nearly linear (Cd-C-Nbcidge= 177”). The large cation appears to be necessary to stabilize the discrete anion rather than the polymeric structures found when smaller cations are used. The use of [SbPh,]+ as the cation led15 to stabilization of the [Cd(CN),I2- anion in the form of polymeric chains with all the cyanide ligands bridging to other octahedral cadmium atoms. N N N1% I \ N N (3) Control of pH was also foundI6 to be a factor in the reaction of cadmium chloride K,[Cd(CN),] sodium citrate and pyridine to give [Cd(py),][Cd(CN),] (4) and [{Cd(CN)(py)2)3][Cd2(CN)7] (5),the latter requiring a lower pyridine concentration.The tetrahedral anions of (4)form cyanide bridges to the cations giving octahedral coordination at the cation with the pyridine ligands in trans disposition. The anion of (3,similar in dimensions to that of (3) also provides cyanide bridges to the cadmium atoms of the cations making them octahedral. P.J. Craig D. Mennie M. Needham N. Oshah 0.F. X. Donard and F. Martin J. Organomet. Chem. 1993 447 5. ’’ J.E. House Jr. and N. E. Kob Znorg. Chem. 1993 32 1053. l4 T. Kitazawa and M. Takeda J. Chem. Soc. Chem. Commun. 1993 309.Is T. Kitazawa M. Akiyama M. Takahashi and M. Takeda J. Chem. Soc. Chem. Commun. 1993 1112. l6 H. Yuge and T. Iwamoto J. Chem. Soc. Dalton Trans. 1993. 2841. Zn Cd and Hg A similar reaction in neat propionitrile gave' K[Cd4(CN),].3EtCN. X-Ray structural determination showed a three-dimensional framework with tetrahedral and octahedral centres in the ratio 3 1 while solid state '13Cd NMR spectroscopy indicated that there is disorder in some of the bridging cyano groups. The X-ray structural determination of [Cd(C6F5),] showed'* it to be two-coordinate with no Cd-F contacts shorter than the sum of the van der Waals distances. The structure of chloro(diacetylmethy1)mercury has'g Hg-Cl and Hg-C bond distances of 2.329 and 2.1 18,respectively as expected from previous determinations on compounds of this type.However the C-Hg-Cl moiety deviates significantly from linearity (161 .lo) due to mutual interaction with the oxygen atoms of a second molecule (Hg-0 = 2.57 and 2.698,). The carbonyl vibrational frequencies in the IR spectrum are weak probably as a result of this interaction. Bis[ (dimethylisopropoxysilyl)methyl]zinc crystallizes in a structure characterized2' by intermolecular coordination of oxygen to zinc leading to a helical polymer with zinc in a trigonal planar configuration (Zn-0 = 2.2528,). The a-CHSi group of (6) prepared2' by metathesis of the corresponding lithium salt and [ZnCl,] showed a remarkably low field-shift of 13ppm in the 13C NMR spectrum and small coupling constants 'J("C-'H) and 'J('3C-29Si) attributable to some sp2 character at this carbon atom.Complexation with bipy to give (7) led to a strong high-field shift for the a-carbon atom. / -Si-4 Nitrogendonor Ligands [Hg{N(S02Me)2}2] (8) and [Hg2{N(S02R)2)2] CR = Me (9) C6H4C1 -41 are formed2 as sparingly soluble precipitates when dilute nitric acid solutions of mercury(1r)- and mercury(1)-nitrates are added to aqueous HN(SO,R) . Compound (8) formed the complexes [Hg{N(SO,Me),),L,] (L = dmso (lo) MeCN dmf py phen) and [Hg(N(SO,Me),),(hmpa)] (11)readily. Attempts to form complexes of (9) with these additional ligands led to disproportionation to mercury(o) and the " T. Kitazawa H. Sugisawa M. Takeda and T. Iwamoto J. Chem. Soc. Chem. Commun. 1993 1855. Is H.Strasdeit I. Busching A.-K. Duhme and S. Pohl Acta Crystallogr. Sect. C 1993 49 576. l9 P. Toledano C. Bonhomme M. Henry and J. Livage Acta Crystallogr. Sect. C 1993 49 1916. 2o H.-J. Gais G. Bulow and G. Raabe J. Am. Chem. SOC. 1993 115 7215. M. Westerhausen and B. Rademacher J. Organomet. Chem. 1993,443 25. 22 A. Blaschette P.G. Jones A. Michalides and K. Linoh Z. Anorg. A&. Chem. 1993 619 392. 94 H. Sloan mercury(I1) complexes. All of (8),(lo) and (11) contain linear or nearly linear N-Hg-N moieties the angles and Hg-N distances being 176.3' and 2.067 A 180" and 2.072 A and 170.5' and 2.057/2.067 A,respectively. The structure of (10)is trans-square planar with the Hg-0 bond being 2.612 A. Compound (1 1) is a slightly distorted T-shape with a Hg-0 bond distance of 2.462 A and there is secondary coordination in the crystal to three sulfonyl oxygen atoms for each mercury atom.The preparation and NMR spectra of a number of bis(pheny1)mercury derivatives bearing suitably oriented 2-pyridyl or 2-pyrazole substituents have shown2 a tendency for weak interactions between the aromatic nitrogen and the mercury atoms. The X-ray structural determination of bis{2-(pyridin-2'-yl)phenyl)mercury (12) revealed coplanar phenyl rings with linear C-Hg-C bonding. The parallel pyridyl groups are twisted slightly out of this plane (10.8'). The linear N-Hg-N moiety has Hg-N bond distances of 2.798 8 which are much longer than those formed by simple heterocyclic nitrogen donors. The reaction of the organometallic (13) with MC1 (M = Zn Cd Hg) gave24 complexes where the dimeric cadmium compound (14) was shown to have rare five-coordination.fi2 /p\ (W)&r CH-CH2NHCH2CH2NMe 'P/ fi2 (13) Both of the complexes [ZnClL] and [ZnL,] (15) (L = hydridotris(3-phenyl-pyrazoly1)borate) contain'' a tetrahedral zinc centre. In (15) ligand L is bidentate with N-Zn-N angles of 101.5 102.7 113.9 and 118.9'. Complex (15) was prepared by the decomposition of [Zn(OR)L] (R = H alkyl) and a further product of these reactions is a cationic complex of the form [Zn(3-phenylpyrazole)L] + . 23 D. St.C. Black G. B. Deacon G. L. Edwards and B. M. Gatehouse Aust. J. Chem. 1993 46,1323. 24 Haupt E. Kleineberg and U. Florke Z. Anorg. Allg. Chern. 1993 619 869. H.-J.25 F. Hartmann W. Klaui A. Kremer-Aach D. Mootz A. Sterath and H.Wunderlich Z. Anorg. Allg. Chem. 1993,619 2071. Zn Cd and Hg The reaction of the arsazene (16) with [M{N(SiMe,),),] (M =Zn Cd) gave26 the heteroallyl complex (17). The two planar four-membered rings are linked to give distorted tetrahedral geometry at the metal atom (the torsion angle between the rings for Zn is 62.9"and for Cd 51.8'). This distortion is not related to the steric effect of the substituents on the ligands. The M-N and As-N bond lengths are typical of single and double bonds respectively. (17) (M =Zn,Cd) The reaction of [ZnR,] (R =Me Et N(SiMe,),) with HN{P(NMe,),NSiMe,) gave27 the cyclozincaphosphazene (18). An X-ray analysis showed the six-membered ring to be twisted and the zinc atom to be trigonal planar.NMR spectroscopy showed the equivalence of the phosphorus atoms. M%N NM%SiM% \/ 1 NrN\ /SiMq \ /""-"\SiMe, 7\-N\ M%N NM%SiMg 5 Other Pnictidedonor Ligands Electrospray mass spectral studies on [Hg(PR,),X,] (PR =monodentate phos- phine X =CIO, CF,COO) have shown28 the tendency for these complexes to form 26 U. Wirringa H. W. Roesky M.Noltemeyer and H.-G. Schmidt Angew. Chem.,Int. Ed. Engl. 1993,32 1628. "S.K. Pandey A. Steiner H. W. Roesky and D. Stalke Inorg. Chem. 1993 32 5444. 28 R. Colton and D. Dakternieks Inorg. Chim. Acta 1993 208 173. 96 H. Sloan triphosphine adducts that readily lose a phosphine ligand demonstrating the mechanism of phosphine exchange in these systems.The phospholes dmpp and dbp were reacted,' with [HgX,] (X = C1 Br I) in 1 1 and 2 1 mole ratios. Complexes with both 1 1 and 2 1 stoichiometries were obtained though the 2 1complex of dmpp/HgCl is very unstable and readily dissociates to the 1 1 complex. The relative stability of these complexes contrasts with the simpler phosphine analogues prepared from PPh or PEt which are all stable and from PBu which does not give stable 2 1 complexes for X = Br or I. X-Ray structural determinations showed that [Hg(dbp),Br,] is mononuclear and tetrahedral. Both [Hg(PPh,),Br,] and [Hg(dmpp)I,] are symmetric binuclear complexes with two bridging halogen atoms though the bromine complex showed the phosphine ligands to be magnetically inequivalent.[Hg,(PBu,),I,] is an unsymmetrical binuclear complex. The 31PNMR spectra of 1 1 solutions of tmpp and [HgX,] (X = C1 Br I) in + MeCN revealed3' the presence of both [HgX(tmpp)] and [Hg(tmpp),I2'. The proportion of the first of these two species relative to the second increases in the sequence C1 < Br < I. Crystals of [Hg(tmpp),][Hg,Cl,] were isolated and the cation shown to have a near linear P-Hg-P (166.51') moiety the deviations from linearity being associated with methoxy oxygen/mercury contacts. Tetrahedral mercury occurs in the symmetrical anion with two bridging chloride ligands. The far-IR spectra of other solids isolated showed the presence of similar [Hg,XJ2- (X = Br I) anions. The reaction of HP(SiMe,) and [M{N(SiMe,),},] (M = Zn Cd Hg) gave31 the dinuclear complexes [M,{P(SiMe,),),{p -P(SiMe,),),] (19).The zinc and cad- mium complexes (19)gave symmetric bridging phosphido groups with the metal atoms being distorted trigonal planar; the central M,P moiety is essentially square. Steric interaction of the SiMe groups of each bridge with one of the terminal phosphide ligands appears to cause different PI-M-P angles (M = Zn 144.9 124.1'; M = Cd 146.7 124.3'). In contrast the mercury complex (19) contains asymmetric phosphido bridges the longer Hg-P distance of 3.246A being only marginally shorter than the sum of the van der Waals radii (3.35A) and the basically linear P-Hg-P of the two halves of the dimer is little affected (175.8'). The two Hg-P distances in the 'halves' are similar (2.402,2.410A).The zinc and cadmium complexes (19)are dimeric in solution and undergo bridging-to-terminal site exchange. The mercury complex is monomeric. Metalation of PHCy with [ZnEt,] in thf gave3 the complex [{Zn(Et)(p- PCy2)},(thf)].2thf. The structure was shown to contain a chair-shaped Zn,P ring in which one zinc atom bearing a thf ligand is tetrahedral and the other two zinc atoms are three-coordinate. The admantane-like complexes [M,Cl,(PPh,),(PPr",),] (20; M = Zn Cd) were formed3 by the reaction of MCl with Ph,PSiMe and PPr:. The reaction of [MRX] (M = Zn R = Me Bu' X = C1; M = Cd R = Me X = Br) with LiAsBu; gave34 [M(R)(AsBu\)] (M = Zn Cd R = Me n = 3; M = Zn R = But n = 2).The cadmium compound is less stable than the zinc compounds and 29 G.A. Bowmaker H. J. Clase N.W. Alcock J. M. Kessler J.H.Nelson and J. S. Frye Znorg. Chim.Acta 1993 210 107. 'O L.-J. Baker G. A Bowmaker B. W. Skelton and A. H. White J. Chem. Soc. Dalton Trans. 1993 3235. 31 S.C. Goel M.Y. Chiang D.J. Rauscher and W. E. Buhro J. Am. Chem. SOC. 1993 115 160. '' A. J. Edwards M. A. Paver P. R. Raithby C.A. Russell and D. S. Wright Organometallics 1993,12,4687. 33 A. Eichhofer J. Eisenmann D. Fenske and F. Simon Z. Anorg. Allg. Chem. 1993 619 1360. 34 T.J.Groshens K.T.Higa and R. J. Butcher J. Organomet. Chem. 1993 463 97. Zn Cd and Hg a a I I this method failed to isolate similar mercury compounds though the intermediates [HgRX] are stable and easily prepared. The complex [Cd(Bu')(AsBu\)] was observed in solution by NMR spectroscopy but could not be isolated.[Zn(Bu')(AsBu~)] is a centrosymmetric dimer with planar three-coordinate zinc atoms. The Zn,As ring is square and planar with the Zn-As bond distance of 2.506A consistent with single bonds. 6 Oxygendonor Ligands The reactions of 1 1 molar quantities of eo3 and CdX (X = C1 Br I) in MeCN/MeOH gave3' three different complexes [Cd2(eo3),(p-eo3)]*2H,O (21) in which the bridging ligand coordinates through two oxygen atoms at each six- coordinate cadmium atom; [Cd,Br4(eo3),] (22) which has seven-coordinate cad- mium with two bridging bromo ligands; and [Cd(eo3),][Cd14] which contains an eight-coordinate cadmium atom in the cation. A boiling methanolic solution of 7-azaindole added to methanolic zinc acetate followed by triethylamine gave36 the colourless [Zn,O(C,H,N,),].This has a core of four zinc atoms arranged tetrahedrally about the oxygen atom with each zinc atom connected by a bridging 7-aza-indolate ligand to each other zinc atom (23). At room temperature the complex displays intense photoluminescence at 448 nm in the solid state and 425 nm in MeCN with the lifetime and quantum yield of the emission being 0.1 ps and 0.17 respectively. The long lifetime suggests a spin-forbidden transition. The Zn-Zn distance in the crystal is greater than twice the usual van der Waals radius for zinc at 3.147 to 3.209A. Treatment of zinc perchlorate and tmpa in MeOH with one equivalent of KOH gave3 the colourless perchlorate of (24) in nearly quantitative yield.Solutions of (24) readily absorb CO, even in the low concentrations found in the air to form (25)which exhibits a novel tridentate coordination mode of the carbonate ligand. The reaction of [Co3(C0),{pL,-C( 1,4-C6H4CH,CH,COOH))] (denoted X) with [ZnEt,] gave38 [ZnX,] which is analogous to the reaction of simple carboxylic acids 3s R. D. Rogers A.H. Bond S. Aguinaga and A. Reyes Inorg. Chim. Acta 1993 212 225. C.-F. Lee K.-F. Chin S.-M. Peng and C.-M. Che J. Chem. Soc. Dalton Trans. 1993 467. 37 N.N. Murthy and K. D. Karlin J. Chem. SOC. Chem. Commun. 1993 1236. W. Cen K. J. Haller and T. P. Fehlner Inorg. Chem. 1993 32,995. 98 H. Sloan such as AcOH with [ZnEt,]. However the precursor [Co,(CO),(p3-CCOOH)] where there is direct electronic interaction of the tricobalt cluster with the carboxylate fragment gave (26) in high yield at room temperature.(24) (23) (N'-N7 = 7-azaindole) G (26) [G = CCO~(CO)~] The complexes tr~ns-[M(thf)~(acac),] (27 M = Ni Co Mg) reacted39 with zinc chloride to form [M(thf)2(p-acac),ZnC1,1. The octahedral and tetrahedral centres of these complexes are connected by tridentate oxygen atoms forming part of a four-membered ring { MOZnO}. Mercury(I1) chloride reacted with (27) as tetrafunc- tional Lewis bases to give [M(thf),(p-acac),(HgCl,),]. In these complexes the C1-Hg-Cl moiety is almost linear. [M(acac),] (M = Zn Hg) reacted with cobalt chloride forming [Co(thf),(acac)(p-C1)MClJ with a similar Co-Cl-M-0 ring. In the mercury complex the mercury atom is more nearly tetrahedral (the CI-Hg-Cl angle involving the terminal chlorine atoms is 143.7').A crystal structure determination of [Zn(PhC(O)NC(Se)NEt,),] showed4' it to be a distorted tetrahedral mononuclear complex. The corresponding cadmium complex was found to be dimeric4' with the oxygen atom of one of the chelates on each cadmium forming a bridge to the other cadmium atom. Thus cadmium exhibits an unusual coordination of five in a trigonal bipyramid structure (28) with the axial positions 39 M. Doring E. Uhlig K. Brodersen and A. Wolski Z. Anorg. Ally. Chem. 1993. 619 753 40 W. Bensch and M. Schuster Z. Anorg. Allg. Chem. 1993,619 786. 41 W. Bensch and M. Schuster Z. Anorg. Ally. Chem. 1993 619 791. Zn Cd and Hg 99 occupied by oxygen atoms.Similar bridging by sulfur atoms to give five-coordinate cadmium was also found4 in [Cd(3-Me3Si-pyt),] (29) prepared by electrochemical oxidation of a sacrificial cadmium anode in an acetonitrile solution of 3-trimethylsilyl- pyridone-2-thione. The difference between the Cd-Sbtidge distances is small but significant [2.667(2) and 2.597(2) A]. The trigonal bipyramid form is severely distorted as the apical nitrogen atoms are drawn away from the ideal positions by the small bite angle of the chelate (N-Cd-N = 158.1'). CN 0 N3" /-(28) n (Se 0 = N,N-diethyl-N'-benzoylselenoureate) (29) [N S = 3-Me3Si(pyt)] 7 Other Chalcogenide-donor Ligands The volatile complex Zn(SAr) (Ar = 2,4,6-tri-t-butylphenyl) has been found43 to be dimeric in the solid state with each trigonal-planar zinc coordinated to three thiolato ligands two of which are asymmetric bridging ligands.EHMO calculations indicate negligible Zn-S (pn-pn) interaction. Solid-state ' ' ,Cd NMR studies have shown44 the shielding-structure correlations over a range of mono- di- and tetra-nuclear cadmium-sulfur complexes. The reactions of polymeric [M(btt),] (M = Zn Cd) with py bipy or phen gave4' mononuclear adducts. The species [Zn(btt),L,] (30; L = (py), bipy phen) have distorted tetrahedral ZnN,S cores with the zinc atoms coordinated to the exocyclic sulfur atoms of btt. There is no evidence of coordination of the sulfur and nitrogen atoms of the heterocyclic ring of btt to zinc. The complex [Cd(btt),(py),] showed a distorted octahedral environment for the CdN4S core the btt ligands coordinating through the exocyclic sulfur and the heterocyclic nitrogen atoms.The exocyclic sulfur atoms are trans to each other with cis pyridine ligands. The reaction of cadmium nitrate NaSOCPh and [NMe4]C1 in aqueous MeOH gave46 [NMe,][Na(Cd(SOCPh),),] (31). An X-ray structural determination has revealed a distorted octahedral NaO centre with each cadmium atom having almost planar trigonal coordination to three sulfur donors. The Cd-0 distances for the sodium-coordinated oxygen of each ligand are in the range 2.659 to 2.825 A suggesting 42 R. Castro J. A. Garcia-Vazquez J. Romero A. Sousa A. Castiiieiras W. Hiller and J. Strahle Inorg. Chim. Acta 1993 211 47. 43 M. Bochmann G. Bwembya R. Grinter J.Lu K. J. Webb and D. J. Williamson Inorg. Chem. 1993,32 532. 44 J. Sola P. Gonzalez-Duarte J. Sanz I. Casals T. Aha 1. Sobrados A. Alvarez-Larena J.-F. Piniella and X. Solans J. Am. Chem. SOC. 1993 115 10018. 45 R. Baggio M.T. Garland nd M. Perec J. Chem. Soc. Dalton Trans. 1993 3367. 46 J. J. Vittal and P. A. W. Dean Inorg. Chem. 1993 32 791. 100 H. Sloan some interaction between cadmium and oxygen atoms. The 23Na NMR spectra shows that dissociation into Na+ and cadmium complex anions takes place in solution and "'Cd NMR spectra are consistent with bonding of cadmium to both sulfur and oxygen ligand atoms. Solid-state '13Cd NMR of three structural isomers of the anion [Cdl,S,(SPh)l,]4- + + (32) in the "Me,] and [NHEt,] salts have been c~rrelated,~ with variations in the basic structure due to configurational isomerism of the (p-SPh) ligands and crystal packing variations at the periphery of the clusters.Variations in the chemical shift data correlate principally with the S-Cd-S angle. SR 1" I 'SR NMR spectra for a number of complexes (33) have been reported.48 The chemical shifts for 77Sebound to the metal atom in the zinc and cadmium complexes occur at higher fields than those for the corresponding diselenocarbamato- and 1,l-dis-elenolato- complexes. This is in contrast to the reverse effect seen in transition metal complexes. 47 G.S. H. Lee K. J. Fisher A.M. Vassallo J. V. Hanna and I.G. Dance Inorg. Chem. 1993.32 66. 4E G. Matsubayashi and A. Yokozawa Inorg.Chim. Acta 1993 208 95. Zn Cd and Hg (33) (M = Zn,Cd) The reaction of Na,Se4 with mercury acetate and 15-crown-5 in dmf followed by recrystallization in the presence of 12-crown-4 gave4' dark red needles of CNa(l2- crown-4),][Hg(Se4),].1 Sdmf. The mercury atom in the anion has a distorted tetrahedral structure the anions being arranged in infinite chains via Se . Se contacts. The reaction of [Zn(CH,SiMe,),] and HSe(mes*) gave5' [Zn(CH,SiMe,)(Se(mes*)}] containing a six-membered ring of alternating zinc and selenium atoms. This ring is twisted in contrast to the planar ring of the sulfur analogue. Solutions of [M(OAc),] (M = Zn Hg)and 15-crown-5 in dmf treated with K,Te in dmf at 0 "C (M = Zn) and -50 "C (M = Hg) gave5' black crystals of [K( 15-crown- S),][MTe,].The complex [ZnTe,12- (34) has a [Te412- chelate and a [Te,12- ion bonded through a terminal atom the disposition about zinc being not quite planar (the sum of the Te-Zn-Te angles = 378.2') whereas the [HgTe,12- (35) anion has a triply bonded Te,moiety which is trigonal planar about mercury(I1). The symmetrical Te-Te-Te grouping about the middle coordinated tellurium atom of (35) is very nearly linear (173.3") and the Te-Te bonds within this moiety are longer than the other Te-Te bonds. Compound (35) was also ~ynthesized~~ by the addition of a polytelluride solution prepared by dissolution of tellurium powder and Li,Te in dmf to [Hg(S,COEt) and [PPh4]C1 in dmf and heating the mixture with triethyl phosphine to give [PPh,],[HgTe,].The anion (35) which again exhibits some disorder was found to have similar dimensions (Te-Te-Te angle of 174.52') to those in the [K( 15-crown-5),] compound. 1'-Tt? (35) (34) The reaction of Na,Te with cadmium acetate and 15-crown-5 in dmf gave53 [Na( 15-crown-5)][Cd4Te ,]-8dmf. The centrosymmetric anion (36) contains p2-Te p4-Te2 and ~2-Te3 units. The complex tris(2-telluro-5-methylthiophene)mercury(11) was to have a trigonal planar arrangement of the tellurium atoms about mercury. The methyl substituent avoided the rotational disorder that can occur with the parent ion 2-tellurothiophene. 49 A. Ahle K. Dehnicke K. Maczek and D. Fenske Z. Anorg. Allg. Chem. 1993 619 1699. K. Ruhlandt-Senge and P. P. Power Inorg. Chem. 1993 32 4505.U. Miiller C. Grebe B. Neumiiller B. Schreiner and K. Dehnicke Z. Anorg. Allg. Chem. 1993,619 500. '* J. M. McConnachie M. A. Ansari J. C. Bollinger R. J. Salm and J. A. Ibers Inorg. Chem. 1993,32 3201. 53 B. Schreiner K. Dehnicke and D. Fenske Z. Anorg. Allg. Chem. 1993 619 1127. 54 J. Zhao J. W. Kolis and W.T. Pennington Acta Crystallogr. Sect. C 1993 49 1753. 102 H. Sloan 1-RR Ye\TeOTe (38) (R=CF3) 8 Halogen-donor Ligands The tetrabromozincates M,[ZnBr,] (M = Li Na) have been prepared." In contrast to Li,[ZnCl,] these new compounds with olivine type structures do not undergo any phase transition between 20 "C and their melting points. Diiodobis( l-pyrroline)zinc(~~)~~ was shown to adopt a distorted tetrahedral struc- ture with a plane of symmetry passing through the zinc and nitrogen atoms.One of the pyrroline ligands lies in the plane of symmetry and the other is perpendicular to it. The I-Zn-I angle is 120.3" to minimize 1.e.I interaction. Both Zn-N and Zn-I bond distances are close to those of the similar pyridine complex. The compounds [(PhMe,Si),CMCI] (37; M = Zn Cd Hg) have been prepareds7 by reaction of Li[C(SiMe,Ph),] with MCl,; for zinc and cadmium they were obtained via the intermediates [MC(SiMe,Ph),(pCl),Li(thf),]. The zinc and cadmium com- pounds form dimers [{ MC(SiMe,Ph),},(p-Cl),] in the crystal and the cadmium compound is also dimeric in solution. In the solid state the three-coordinate planar metal atoms have angles C-M-CI and CI-M-Cl of 136" and 88" (M = Zn) and 137" and 86" (M = Cd).The chloride bridges are slightly unsymmetrical. The mercury compound (37; M = Hg) is also dimeric in the crystal but the geometry is almost that of separate two-coordinate molecules (C-Hg-CI 171.0 and 171.3') with a very weak Hg * * * C1 interaction (mean distance 3.29 A). The complex (38) formed58 complexes with [PPh,]X (X = C1 Br) of the form [{HgC(CF3),),X2I2-. An X-ray structural determination of the chloride complex showed that the two chlorine atoms are located above and below the ten-membered ring of (38) and that both are bound to all five mercury atoms. While there is some variation in the Hg-Cl bond distances they are all significantly shorter than the sum of the van der Waals radii as is also the C1-Cl distance through the middle of the ring.55 A. Pfitzner J. K. Crockcroft I. Solinas and H. D. Lutz Z. Anorg. Allg. Chem. 1993 619 993. 56 A. A. Freer G. McDermott J. C. Melville and D.J. Robins Acta Crystallogr. Sect. C 1993 49 2115. '' S. S. Al-Juaid C. Eaborn A. Habtemariam P. B. Hitchcock,J. D. Smith K. Tavakkoli and A. D. Webb J. Organomet. Chem. 1993 462 45. '13 V. B. Shur I. A. Tikhonova F. M. Dolgushin A. I. Yanofsky Yu.T. Struchov A. Yu. Volkonsky E.V. Solodova S.Yu. Panov P. V. Petrovskii and M. E. Vol'pin J. Organomet. Chem. 1993 443 C19.

ISSN:0260-1818    

DOI:10.1039/IC9939000091

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

9 Inorganic and Organometallic Polymers By I. MANNERS Department of Chemistry University of Toronto 80 St. George St. Toronto M5S 1A1 Ontario Canada Macromolecules containing main group elements or transition metals as part of the main chain structure continue to attract considerable attention because of their interesting and unusual properties and also their potential applications as speciality materials.lP1 This review focuses on developments in inorganic and organometallic polymer chemistry during the year 1993. The review has the same format and follows on from previous articles7y8 in the series which cover the years 1991 and 1992. The first sections of the review cover new developments concerning the well-established inorganic polymer systems namely the polysiloxanes polyphosphazenes and poly- ~ilanes.~ A brief introduction to each of these classes of inorganic polymer systems was included in the appropriate sections of the first article of this ~eries.~ Following these sections recent developments concerning other polymers based on main-group elements and transition metals are discussed.As with previous articles in this series the main emphasis is placed on polymers with inorganic elements within the main chain rather than in the side-group structure. 1 Polysiloxanes (Silicones) Polysiloxanes continue to be the focus of considerable attention particularly liquid crystalline materials.’ ’-’ Phthalocyaninantopolysiloxanessuch as (1) represent a very interesting example of a rigid rod macromolecular system with flexible alkoxy side chains which dramatically ‘Silicon-Based Polymer Science’ ed.J M. Zeigler and F.W.G. Fearon Advances in Chemistry 224 American Chemical Society Washington D.C. 1990. ‘Inorganic and Organometallic Oligomers and Polymers’ ed. by R. M. Laine and J. F. Harrod Kluwer Publishers Amsterdam 1991. ‘Siloxane Polymers’ ed. J. A. Semlyen and S.J. Clarson Prentice Hall Engiewood Cliffs N.J. 1991. J. E. Mark and H. R. Allcock and R. West ‘Inorganic Polymers’ Prentice Hall 1992. ’ Journal of Inorganic and Organometallic Polymers Plenum New York 1991 onwards. ‘I. Manners Polymer News 1993 18 133. I. Manners Ann. Rep. Prog. Chem. Sect. A Inorg. Chem. 1991 88 77. I. Manners Ann. Rep. Prog. Chem. Sect. A Inorg. Chem. 1992 89 93.I. Manners Ado. Mater. 1994 6 68. lo H. R. Allcock Ado. Mater. 1994 6 106. I’ T. Sauer Macromolecules 1993 26 2057. ’* E. Chiellini G. Galli E. Dossi F. Cioni and B. Gallot Macromolecules 1993 26 849. l3 I.G. Shenouda and L.C. Chien Macromolecules 1993 26 5020. l4 C.S. Hsu L. J. Shih and G. H. Hsiue .Macromolecules 1993 26 3161. I’ R. Fu P. Jing J. Gu Z. Huang and Y. Chen Anal. Chem. 1993 65 2141. 103 104 I. Manners enhance solubility in organic solvents. Sauer has studied the phase behaviour of a series of these polymers and has found three different types of behaviour depending on the side-chain length.’ ’ Short side-chain derivatives do not show any phase transition up to the decomposition temperature. Medium length side-chains lead to polymers which show a transition to a highly viscous liquid crystalline phase.On the other hand polymers with long-chain alkoxy substituents have an additional mesophase at higher temperatures. The rod-like polymer molecules were found to pack in a two-dimensional hexagonal lattice. This hexagonal columnar phase has high thermal stability as a consequence of the cylindrical symmetry and the very high chain stiffness of the polymer structure. The thermal stability of the polymers was found to be limited by side-chain cleavage which takes place in the 250-300”C range. The cleavage mechanism was believed to involve 8-elimination. OR’ OR’ OR’ 0R’ Chiellini et al. have reported the synthesis and properties of new chiral smectic polysiloxanes from mesogenic olefin or vinyl ether monomers.’ Such materials can display optimum values of spontaneous polarization and response time which are comparable to those of small molecule liquid crystals with which they can compete effectively for high information screen applications.Fu and co-workers have reported side-chain liquid crystalline polysiloxanes (2) containing crown ether moieties in the side-group structure which are useful as stationary phases for capillary gas chromatography.” Corriu and co-workers have prepared organic-inorganic hybrid networks via the hydrolysis of alkoxysilylferrocene derivatives such as (3). This leads to silsesquioxane Inorganic and Organometallic Polymers materials (4) which were characterized by IR and solid state I3C and 29Si NMR spectroscopy.Co-hydrolysis of (3) with Si(OMe) leads to hybrid silica gels.16 In other developments concerning polysiloxane chemistry Zeldin and co-workers have described new polymers with pendant pyridyl groups which are of interest as nucleophilic catalysts for acyl transfer reactions. Crivello has reported the synthesis and polymerization of monomers containing epoxy and alkoxysilane groups.' * Riffle has reported the preparation and properties of silicone-oxazoline diblock copolymers.' A particularly novel development involves the synthesis of silsesquioxane-siloxane copolymers (5) from polyhedral dihydroxysilsesquioxanes by Lichtenhan and co- workers.20 This was achieved via the reaction of the latter species with difunctional halogeno- or amino-silanes or oligosiloxanes.The resulting polymers had molecular weights (M,)of 15oo(r200000. These materials have potential as processable preceramic polymers. Preliminary experiments showed that these polymers yield ceramics containing SiO and SiOC when pyrolyzed. 2 Polyphosphazenes Polyphosphazenes are a remarkably diverse class of inorganic macromolecules that continue to attract considerable attention. Allcock and Turner have reported2' interesting studies of the polymerization behaviour of a series of transannular bridged and spirocyclic cyclotriphosphazenes l6 G. Cerveau R.J.P. Corriu and N. Costa J. Non-Cryst. Sol. 1993 163 226. " M. Zeldin E. Granger and W.K. Fife J. Inorg. Organomet. Polym. 1993 3 141. J.V. Crivello and D.Bi J. Polym. Sci. A Polym. Chem. 1993 31 3121. l9 Q. Liu G.R. Wilson R. M. Davis and J.S. Riffle Polymer 1993 34 3030. 2o J.D. Lichtenhan N.Q. Vu J.A. Carter J. W. Gilman and F. J. Feher Macromolecules 1993 26 2141. H. R. Allcock and M.L. Turner Macromolecules 1993 26 3. 106 I. Manners [e.g. (6) and (7)]. These provide a comparison with transannular ferrocenylcyclot- riphosphazenes which undergo ring-opening polymerization to yield high molecular weight polymers. The transannular and spirocyclic species underwent ring-ring equilibration to yield higher cyclics or moderate molecular weight polymers. In some cases trace amounts of N,P,Cl were required for polymerization to occur. The Allcock group has also reported studies of the arene sulfonation of cyclic phosphazenes and the corresponding high polymeric derivatives and full details of work on polyphosphazene interpenetrating polymer network^.^^.^^ Matyjaszewski and co-workers have reported further advances in the use of the anionic copolymerization of phosphoranimines to prepare random polyphosphazene copolymers with alkoxyethoxy and trifluoroethoxy functional groups.24 The phos- phoranimine monomers (8) were prepared via the Staudinger reaction of the appropriate phosphites P(OR) with Me,SiN,.Simultaneous copolymerization of the phosphoranimines using [Bu4N]F as initiator at 133 “C for 13 h yielded a series of random copolymers (9) which were characterized by 31PNMR ‘H NMR gel permeation chromatography and differential scanning calorimetry.The resulting copolymers possessed monomodal molecular weight distributions with M = 10000-150000 and M = 8000-100000. In addition the solubilities and thermal and mechanical properties were found to be dependent on the repeat unit ratios. Allcock and co-workers have reported the synthesis of polyphosphazenes (10)with Fe(CO),Cp side groups via the reaction of lithiated poly(ary1oxyphosphazenes) with F~I(CO),CP.~ Similar surface modification reactions were carried out on cross-linked films of [NP(p-OC,H,Br),], by treatment initially with BunLi and then with the same iodo-organoiron species. The surface metallated materials were characterized by scanning electron microscopy and X-ray microanalysis along with other techniques. ” H. R. Allcock E.H. Klingenberg and M. F. Welker Macromolecules 1993 26 5512. 23 H. R. Allcock K. B. Visscher and I. Manners Chem. Muter. 1992 4 1188. 24 K. Matyjaszewski M. S. Lindenberg M. K. Moore M. L. White and M. Kojima J. Inorg. Organornet. Polym. 1993 3 317. ’’ H. R. Allcock E.N. Silverberg C.J. Nelson and W. D. Coggio Chem. Mater. 1993 5 1307. Inorganic and Organometallic Polymers L Majoral Bertrand et al. have reported a route to poly(ally1phosphazenes) from poly(dichlorophosphazene).26 This new method for introducing organometallic side-groups to phosphazenes involves the photochemical reaction of allyltri(n- buty1)stannane with [NPCl,] (Equation 1). Intrinsic viscosity measurements showed that the phosphorus-nitrogen skeleton had not been cleaved to a significant extent.This is important as the reaction of most organometallic reagents with poly(dich1orophosphazene) leads to skeletal cleavage as well as substit~tion.~’ Crumbliss Wisian-Neilson and co-workers have reported studies of the redox properties of a series of polyphosphazenes with pendant ferrocenyl groups. The polymers were synthesized by side-group modification of poly(phenylmethy1phos- phazene) (Equation 2).28The latter was prepared by the condensation polymerization of a phosphoranimine precursor. The electrochemical studies of the polymers in solution or as films on an electrode indicated increasing charge-transfer efficiency with the number of ferrocene groups present. This is consistent with an increasing contribution from electron-hopping between the metallocene groups.In another development concerning polyphosphazenes detailed analyses of the physical properties of aryloxy-substituted copolymers including studies of stress-strain isotherms and thermoelasticity have been carried out by Mark et a/.29930 26 H. Rolland P. Potin J. P. Majoral and G. Bertrand Inorg. Chem. 1993 32,4679. ’’ H.R. Allcock J. L. Desorcie and G.H. Riding Polyhedron 1987 6 119. 28 A. L. Crumbliss D. Cooke J. Castillp and P. Wisian-Neilson Inorg. Chem. 1993 32,6088. 29 G.B. Sohoni and J. E. Mark J. Inorg. Organomet. Polym. 1993 3,331. 30 J.E. Mark and G.B. Sohoni J. Inorg. Organomet. Polym. 1993 3 347. 108 1. Manners Ph (1) 6u"LI tt=Nk Me 3 Polysilanes Polysilanes continue to attract intense interest from both fundamental and applied perspectives.The remarkable properties of polysilanes has led to their use in electroluminescent devices. For example light emitting diodes (LEDs) which utilize poly(methylpheny1- silane) as the hole-transporting material have been reported by Haarer and co- worker~.~ The LED devices comprised three functional polymer layers which were all fabricated by wet spin-coating processes (hole-transporting emissive and elec- tron-transporting) and two electrodes (Figure 1). The high hole-mobility in poly(methylphenylsi1ane) compared to other organic photoconductors is a conse- quence of the a-delocalized structure. aluminium electrode 30 wt% PBD in polystyrene 1.5 wt% DCM in polymethylphenylsilane polymethylphenylsilane indium tin oxide electrode strate Figure 1 The LEDs fabricated were found to electroluminesce at a threshold voltage of ca.40V in a continuous DC mode under forward bias. The light from the LED devices was yellow and was easily observed in a dark room. The emissive layer consisted of poly(methylphenylsi1ane) doped with 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM). The electroluminescence spectra for the device and the photoluminescence spectrum of DCM were extremely similar. This supported the idea that the electroluminescence of the device arises from the decay of the singlet excited state of the DCM molecules in the emissive layer which is generated by the recombination of holes and electrons injected from the two electrodes.The high operating voltages for the devices (ca. SCrlOOV)led to lifetimes of less than 1 h. However the authors are optimistic that the device performance can be considerably improved by optimization of the structure especially the layer thickness and the choice of electrode materials. The authors also note that poly(methylphenylsi1ane)shows a 31 H. Suzuki H. Mayer J. Simmerer J. Yang and D. Haarer Adu. Mater. 1993 5 743. Inorganic and Organometallic Polymers high effective mobility of holes compared to poly(phenyleneviny1ene) (PPV) which has been used previously for polymer-based LED fabrication. Thus this particular polysilane might be useful for fast switching applications. In addition the lack of a visible absorption for poly(methylphenylsi1ane)makes this material attractive for the fabrication of LEDs in the whole range of the visible spectrum including the blue region as reabsorption of electroluminescent light does not occur.In a separate Hadziioannou and co-workers have shown that the incorporation of well-defined polysilane segments in poly (thiophenes) allows the tuning of the photo- and electro-luminescence of the resulting multiblock copolymers [e.g. (11) M = 14280 M = 68001. The band gap of the oligothiophene blocks strongly depends on delocalization length as inferred from the blue shift of the absorption maxima when the number of thiophene rings is decreased. In contrast a change in the length of the larger band gap oligosilane block had only a minor effect on the absorption maximum.This indicated that only weak coupling occurred between the o-conjugated oligosilane blocks and the 7t-conjugated oligothiophene blocks along the main chain. Studies of the photoluminescence of the copolymers confirmed that the oligothiophene block was the active unit. Electroluminescent devices were made from the copolymers which emit light with colours ranging from blue to orange-red depending on the length of the oligothiophene block. Significantly some of the fabricated devices showed no apparent degradation after seven months. Studies by Wang and West33 have shown that poly(methylphenylsi1ane)doped with fullerenes greatly increases the photoinduced charge-generation efficiency. The combination of high charge-generation efficiency and high carrier mobility makes such materials one of the best polymeric photoconductors known.Pure poly(methylpheny1- silane) was found to have very low charge-generation efficiency and no surface discharge was detected when a film was irradiated with a tungsten lamp. However for a film of the same polysilane doped with fullerenes (1.6%) the photoinduced discharge rate was enhanced by orders of magnitude. The low field-charge-generation efficiency was found to be about an order of magnitude better than for fullerene-doped poly(vinylcarbazo1e) but less than that of thiapyrylium dye aggregate doped amine/polycarbonate photoconductor which is generally regarded as the best commercial polymeric photoconductor. However at higher field the charge-gener- ation efficiency of the fullerene/polysilane photoconductor is greater than the latter.Attempts to extend this approach to other polysilanes such as poly(cyclohexylmethy1- silane) and poly(dimethylsi1ane) were unsuccessful and no significant photoinduced discharge was observed for these polysilanes even after doping with fullerenes. This result is surprising in view of the previously demonstrated mobility of photoinduced 32 G.G. Malliaras J.K. Herrema J. Wildernan R.H. Wieringa R.E. Gill S.S. Lampoura and G. Hadziioannou Adv. Mater. 1993 5 721. 33 Y. Wang R. West and C. H. Yuan J. .4m. Chem. SOC. 1993 115 3844. 110 I. Manners holes in these polymers. These results indicate that a specific interaction exists between fullerene and the phenyl group of poly(methylphenylsi1ane) which leads to the formation of a weakly bonded complex which enhances electron-transfer from the polysilane to the fullerene.Other areas of polysilane research are also attracting continued attention. The main method of preparing polysilanes the thermally induced Wurtz coupling of di- chlorosilanes with alkali metals has been the subject of further study. Jones and co-workers have shown34 that the blue colour which develops during this reaction arises from the presence of colloidal alkali metal particles and that these play a role in determining the proportion of the very high molecular weight polymer that is formed. Oligomeric materials that are always generated were shown to be formed uia alkali-metal-induced polymer degradation reactions.The transition metal catalyzed dehydrogenative route to oligosilanes discovered by Harr~d~~,,~ continues to attract intense attention (Equation 3). Tilley has reviewed research carried out in his laboratories on the coordination polymerization of silanes to polysilanes involving a a-bond metathesis mechanism.,’ Using certain Zr catalysts poly(phenylhydrosi1ane) with molecular weights of up to ca. M = 100oO and M = 5000 have been produced from PhSiH,. + H2 (3) Waymouth and co-workers have shown that trifluoromethyl-substituted phenyl-silanes undergo dehydrogenative coupling in the presence of zirconocene catalysts to yield poly{ (trifluoromethy1)phenylhydrosilanes)with M = 1000-3000.38 Copoly- merization reactions with phenylsilane allowed the relative rates of polymerization of the trifluoromethyl-substituted phenylsilanes to be deduced.Harrod and co-workers have found that in contrast to the Ti and Zr analogues dimethylhafnocene does not react with PhSiH,.39 This was attributed to the low reactivity ofthe M-C bonds in this species to a-bond metathesis which inhibits the formation of the true catalyst which is believed to be a silyl hydride complex. Tilley has also reported the use of dehyd- rogenative coupling reactions to synthesize disilanylenearylene oligomers and polymers (Equation 4).40 Heating of the reaction mixtures leads to increases in molecular weight which are believed to arise from cross-linking via dehydrocoupling of the ‘backbone’ Si-H groups.Eventually insoluble polymers are formed. These materials gave much higher ceramic yields (ca.67%) on pyrolysis compared to the low molecular weight linear oligomers formed at room temperature. 34 R.G. Jones R. E. Benfield R. H. Cragg A.C. Swain and S. J. Webb Macromolecules 1993 26 4878. 35 C. Aitken J. F. Harrod and E. Samuel J. Organomet. Chem. 1985 279 C11. 36 C. Aitken J. F. Harrod and E. Samuel J. Am. Chem. SOC.,1986 108 4059. 37 T. D. Tilley Acc. Chem. Res. 1993 26 22. 38 J. P. Banovetz H. Suzuki and R. M. Waymouth Organometallics 1993 12 4700. 39 H. Li F. Gauvin and J. F. Harrod Organornetallics 1993 12 575. 40 T. Imori H.G. Woo J. F. Walzer and T.D. Tilley Chem. Muter. 1993 5 1487. 111 Inorganic and Organometallic Polymers In other developments in polysilane chemistry poly(methylphenylsi1ane)-poly-styrene block copolymers have been prepared via the reaction of a,o-dich-loropolysilanes with p~lystyryllithium.~~ The resulting copolymers were characterized by UV/VIS and 29Si NMR spectroscopy and gel permeation chromatography.In addition Schilling and co-workers have investigated the solid state structures phase transitions and thermochromism of polysilane copolymer^.^^ Matsuda et al. have synthesized and investigated the photochemical properties of network and branched polysilanes formed by the copolymerization of MePhSiC1 and PhSiC13.43 4 Other Polymer Systems Based on Main Group Elements The design synthesis and development of new polymer systems containing main group elements in the polymer main-chain continues to attract growing attention.Further studies of poly(thionylphosphazenes) an unusual class of sulphur-nitro- gen-phosphorus polymers which were first reported in 1991 have also been described in the past year6,44*45 and key developments in this area have been reviewed.6 These polymers possess skeletal four-coordinate sulphur(v1) atoms in addition to phos- phorus and nitrogen and are synthesized via the thermal ring-opening polymerization of the cyclic thionylphosphazeiie NSOCl[NPCl,] or the fluorinated analogue NSOF[NPCl,],. The first polyniers with alkoxy side-groups were reported in 1993 (Scheme l).44In addition a6 initio calculations on mimics of poly(thiony1phos-phazenes) suggest that the polynier chain has a cis-trans helical conf~rmation.~~ Full details of the synthesis characterization and properties of a series of representatives of a new class of sulphur-nitrogen polymers the poly(oxothiazenes) which were first reported in 1992 were published by Roy.46 These polymers were produced via the condensation polymerization of N-silylsulfonimidates (Equation 5).The polymerization was found to be catalyzed with Lewis acids and bases and the polymers possess significantly higher glass-transition temperatures than the analogous polyphosphazenes. Theoretical studies indicate that a cis-trans helical conformation is the most stable for these polymers. Further significant advances were also reported in 1993 in the areas of poly(carbophosphazenes) and poly(thioph0sphazenes).These polymers possess back- " s.Demouster-Champagne A. F. de Mathieu J. Devaux R. Fayt and Ph. Teyssie J. Polym. Sci. A Polym. Chem. 1993 31 2009. 42 F.C. Schilling A. J. Lovinger D. D. Davis and F. A. Bovey Macromolecules 1993 26 2716. 43 A. Watanabe H. Miike Y. Tsutsumi and M. Matsuda Macromolecules 1993 26 2111. 44 M. Edwards Y. Ni M. Liang A. Stammer J. Massey G. J. Vancso and 1. Manners Polymer Prepr. (Am. Chem. Soc. Div. Polym. Chem.) 1993 34 324. 45 J. B. Lagowski R. Jaeger I. Manners and G. J. Vancso Polymer Prepr. (Am. Chem. SOC. Div. Polym. Chem.) 1993 34 326. 46 A. K. Roy G.T. Burns G. C. Lie and S. Grigoras J. Am. Chem. Soc. 1993 115 2604. 112 I. Manners X=CIWF X=CIWF X =CI Or F R = OR w OAr Scheme 1 R = Me or Ph bones of phosphorus nitrogen and either three-coordinate carbon or sulphur(1v) Exciting new developments have been reported concerning the macromolecular chemistry of the group 14 elements.For example Bianconi et al. have reported the synthesis of polygermynes which are random network polymers analogous to the previously reported poly~ilynes.~’ The polygermynes were synthesized via the treatment of trichloroorganogermanes with an emulsion of Na/K alloy in pentane in the presence of ultrasound (Equation 6). Na/K pentme; * [RGeI ultrasound The resulting coffee-coloured materials possessed NMR spectroscopic properties similar to those of their silicon analogues. In addition X-ray diffraction showed no peaks and no melting points were detected.The UV/VIS absorptions tail into the *’ H. R. Allcock S. M. Coley I. Manners K. B. Visscher M. Parvez and 0.Nuyken G. Renner,lnorg. Chem. 1993,32 5088. 48 H. R. Allcock J. A. Dodge and I. Manners Macromolecules 1993 26 1. 49 W.J. Szymanski G. T. Visscher and P. B. Bianconi Macromolecules 1993,26 869. Inorganic and Organometallic Polymers visible up to ca. 800nm and account for the deep brown colour. By contrast polysilynes absorb up to 450 nm. In a similar way to polysilynes polygermynes under- go photooxidation to give cross-linked networks of polygermoxanes [RGeO ,Jn. The latter show a characteristic IR band at 846cm-' assigned to Ge-O-Ge stretching. Copolymers containing dyne and germyne units were obtained by copolymerization (Equation 7).These materials were found to possess electronic properties intermediate between those of the two parent homopolymers. For example the UV/VIS absorption of [Bu"Si),~,(PhGe),,,] has an onset at ca. 650nm. The molecular weights of the monopolymers and copolymers. estimated by GPC were in the range of M = 300&15000. A particularly exciting development reported by Tilley and co-workers involves the use of dehydrogenative coupling as a route to p~lystannanes.~' Treatment of neat Bu",nH with CpCp*ZrMe(Si(SiMe,),) yields the polystannane (12) in 93% yield as a yellow solid (Equation 8). Analysis by GPC showed the presence of (presumably) cyclic oligomers and a higher molecular weight fraction with M = 17 500 and M = 7800. The UV/VIS spectrum of the polystannane with M = 7800 possessed a A,, at 382 nm significantly red-shifted compared to the corresponding polygermane.The polystannanes are photosensitive and photobleaching typical of polysilanes and polygermanes was shown to occur. 5 Polymers Containing Skeletal Transition Metal Atoms Polymers containing transition metal atoms in the main-chain structure represent a rapidly expanding area of research with many interesting developments reported in the past year. Poly(metallaynes) which are novel macromolecules with backbones possessing conjugated CEC units and transition metal atoms (M) have been studied in some detail in the past few years. Frapper and Kertesz have reported extended Hiickel calculations to study the electronic structure of polymers of structure (13).' The electronic structures and properties of these materials appear to depend on the size and nature of the oligo-yne bridging ligand the coordination number of the metal T.Imori and T. D. Tilley J. Chem. SOC.,Chem. Commun. 1993 1607. '' G. Frapper and M. Kertesz Inorg. Chern. 1993 32 732. 114 I. Manners (13) and the metal itself. The authors concluded that the best opportunity for high electrical conductivities is provided by a d8 square planar configuration for the transition metal (e.g. M = Pt x = 2) which leads to a larger bandwidth for the conduction band compared to a situation when a d6 octahedral transition metal (e.g.M = Fe x = 4)is present. Advances continue to be made in the area of metallocene-based polymers.Unusual face-to-face metallocene polymers (14) have been reported by Rosenblum and co-workers.” If R = H the dark purple polymer possessed a bimodal molecular weight distribution (with M = ca. 18000 M = ca. 14OOO). If R = Me a partially soluble polymer product resulted with a bimodal molecular weight distribution with a component with M = ca. 139000. Mixed metal polymers containing nickel in addition to iron were also synthesized however these tended to be rather insoluble and the molecular weights were lower. Bulk magnetic susceptibility measurements provided evidence for the presence of nickelocene units in the polymer backbone. Advances have also been reported concerning high molecular weight poly(ferro- cenylsilanes) (16),which were first synthesizeds3 in 1992 by a ring-opening polymeriz- ation route (Equation 9).54-62 The monomers silicon-bridged ferrocenophanes (15) 52 H.M. Nugent M. Rosenblum and P. Klemarczyk J. Am. Chem. Soc. 1993 115 3848. 53 D.A. Foucher B.Z. Tang and I. Manners J. Am. Chem. Soc. 1992 114,6246. 54 W. Finckh R. Ziembinski B.Z. Tang D.A. Foucher D.B. Zamble A. Lough and I. Manners Organometallics 1993 12 823. 55 D. A. Foucher R. Ziembinski B. Z. Tang P. M. Macdonald J. Massey R. Jaeger G. J. Vancso and I. Manners Macromolecules 1993 26 2878. 56 I. Manners J. Inorg. Organomet. Polym. 1993 3 185. 57 B.Z. Tang R. Petersen D.A. Foucher A. Lough N. Coombs R. Sodhi and I. Manners J. Chem. SOC. Chem. Commun. 1993 523. 58 D.A. Foucher and I. Manners Makromol.Chem. Rapid Commun. 1993 14 63. 59 R. Ziembinski C. Honeyman 0.Mourad D. A. Foucher R. Rulkens M. Liang Y. Ni and I. Manners Phosphorus Sulfur Silicon Rel. Elem. 1993.76 219. 6o J. M. Nelson H. Rengel and I. Manners J. Am. Chem. SOC. 1993 115 7035. 61 M.T. Nguyen A. F. Diaz V. V. Dement’ev and K. H. Pannell Chem. Muter. 1993 5 1389. 62 D. A. Foucher,C. Honeyman J. M. Nelson B. Z. Tang and I. Manners Angew. Chem. Int. Ed. Engl. 1993 32 1709. Inorganic and Organometallic Polymers have strained ring-tilted structures. For example (15) (R = Me) has a tilt-angle between the planes of the cyclopentadienyl ligands of 20.8(5)".54 In contrast the corresponding C2lferrocenophane containing an (SiMe,) bridge has a tilt angle of only ca. 4" and appears to be resistant to thermal ring-opening polymerization.heat ___) The synthesis characterization and properties of a series of symmetrically- substituted poly(ferrocenylsi1anes) (16) (R = Me Et Bu" and n-hex) was reported in the first half of 1993.55 UV/VIS studies showed that these materials possess structures which are essentially localized whereas electrochemical studies clearly show that the iron atoms interact with one another. Mossbauer spectroscopic studies of doped samples of (16) (R = Me) are also consistent with an essentially localized electronic structure.56 Poly(ferrocenylsi1anes) have also been shown to function as pyrolytic precursors to magnetic FeSiC ceramics at ca. 500 "C and unusual depolymerization products have also been detected isolated and characterized." In late 1993 studies of more crystalline samples of the previously reported poly(ferrocenylsi1anes) (1 6) (R = Me Et Bun,and n-hex) were also described.61 In 1993 the synthesis of the first examples of poly(ferroceny1germane.s) (1 7)'* and poly(ferrocenylethy1enes)(18)60via ring-opening polymerization routes were also reported.Strained ring-tilted german- ium- and hydrocarbon-bridged ferrocenophanes function as suitable precursors to these materials (Equations 10 and 11). 90-1 50 "C R 116 I. Manners Interestingly electrochemical studies have shown that the iron atoms in poly(ferroceny1germanes)interact with one another in a similar way to those in poly(ferrocenylsilanes).62 In contrast poly(ferrocenylethylenes) which possess a longer two-atom bridge between the ferrocene units possess virtually non-interacting transition metal centres .60*62 New developments concerning polyferrocenylene persulfides which were first reported6 in 1992 have also been described by Rauchfuss and co-worker~.~~ These polymers were synthesized by a novel atom-abstraction induced ring-opening polymerization route.The atom abstraction route using PBu as the desulfurization agent has been extended to the preparation of very high molecular weight (M = 5000&1 OOOOOO) network polymers (19) by using C3lferrocenophanes with two trisulfido bridges as monomers. Poly(ferroceny1enes) are continuing to attract attention with respect to sensor applications. The first examples of the use of poly(ferrocenes) as mediators in amperometric biosensors have recently been rep~rted.~’ Specifically the poly(ferro- cenylmethylenes) (20) (R = H or 2-methoxyphenyl n = ca.12-14) which were synthesized via the condensation of the aldehydes RCHO with ferrocene in the presence of a Lewis Acid are capable of acting as mediators which shuttle electrons between glucose oxidase and a carbon electrode. 63 P.F. Brandt and T.B. Rauchfuss J. Am. Chem. SOC. 1992 114 1926. 64 C.P. Galloway and T. B. Rauchfuss Angew. Chem. Int. Ed. Engl. 1993 32 1319. 65 S. P. Hendry M. F. Cardosi A. P. F. Turner E. W. Neuse Anal. Chim. Acta 1993 281 453. Inorganic and Organometallic Polymers r L Other areas of transition metal polymer chemistry are also attracting attention.Polymers consisting of metallacarborane units ‘polymetallacarborane staircase oligomers’ are of particular intere~t.~~’~’ Studies of oligomers with between 5 and 17 metal atoms [e.g. (21)] consisting of multidecker sandwiches linked by a phenylene group have shown that there is good evidence for electron delocalization within the individual multidecker stacks but that the electronic communication between the stacks is small. The lack of interstack delocalization was attributed to the tilt (ca. 4&60”) of the connecting phenylene spacers relative to the planes of the (methyl- ated)cyclopentadienyl ligands which prevents n-conjugation. This tilt was attributed to the presence of steric repulsions between the methyl groups on the cyclopentadienyl rings and the phenylene moiety.m-0-f I co I co (21) 0 = CR Puddephatt and co-workers have reported full details of an interesting new method for the incorporation of metals into the side-group structure which involves the use of oxidative addition reactions.68 Metalled monomers were prepared uia the reaction of 66 X. Meng M. Sabat and R.N. Grimes J. Am. Chem. SOC. 1993 115,6143. 67 J. R. Pipal and R. N. Grimes Organometallics 1993 12 4458. S. Achar J. D. Scott J. J. Vittal and R. J. Puddephatt Organornetallics 1993 12 4492. 118 I. Manners bromoacetic acid or its derivatives with the platinum(I1) complex PtMe,(bipy). Free radical polymerization subsequently yielded poly(viny1acetate) with pendent organo- platinum groups.Similar polymers were obtained by the esterification of poly(viny1 alcohol) to give poly(viny1bromoacetate) followed by oxidative addition using an excess of PtMe,(bipy). The use of transition metal activated nucleophilic substitution has provided an elegant route to soluble poly(phenylenesu1fide) and poly(pheny1ene oxide) derivatives (22) with pendent Ru(q-C,Me,) groups attached to arene rings in the polymer backbone.69 In addition Cr(CO) groups have been used to solubilize poly(phenyleneterephtha1amide)(PPTA) and these led to a retention of lyotropic liquid ~rystallinity.~' Ru' SO& F3-(22) X = 0or S In the area of rigid rod polymers Puddephatt and co-~orkers~~ have utilized isocyanide-arene-acetylide bidenate ligands to form monomeric and oligomeric gold(1) complexes (23).The latter materials were insoluble in common organic solvents and are probably of low molecular weight.69 A.A. Dembek P.J. Fagan and M. Marsi Macromolecules 1993 26 2992. A. A. Dembek R. R. Burch and A.E. Feiring J. Am. Chem. SOC. 1993,115 2087. G. Jia R. J. Puddephatt J. J. Vittal N. C. Payne Organometallics 1993 12 263.

ISSN:0260-1818    

DOI:10.1039/IC9939000103

出版商:RSC    

年代:1993

数据来源: RSC

摘要:

10 Ti Zr and Hf By S.A. COTTON Felixstowe College Maybush Lane Felixstowe Suffolk IP11 7N0 UK 1 Introduction This report is based on the accessible 1993 literature as well as late 1992 papers. The general pattern of recent reports has been maintained. The importance of some binary compounds seems to be reflected in synthetic work whilst the intensely active area of organometallic chemistry is again treated very selectively. 2 Metallocarbohedranes Bulk production of air-stable Ti8Cl in the solid state has been achieved.' Photodis- sociation mass spectra of Ti,C1 indicate2 metal-atom loss to give Ti,C, (n= 5,6,7) whilst Zr,C, behaves differently affording Zr,C,, Zr6Cl0 Zr5C8 and Zr4C6 as prominent fragments; the cages apparently can decompose either by metal atom loss or elimination of MC,.Quantum cluster local density approximation calculations on Ti,C, indicate3 a negative heat of formation and also stability with respect to decomposition into M and C,. Calculations suggest that a structure with Td symmetry (1)based on a tetracapped tetrahedron with six C units linking the vertices is the most table.^ It has been pointed out that five M,Cl2 clusters can be fused together to give a Ti3,C, cluster. At room temperature Ti8CT2 is reactive6 towards both polar and n-bonding molecules but inert towards oxygen. In addition to the stable M,C ,systems larger species are also observed with up to 60 atoms in the cluster when low-power laser vaporizations are conducted (at high power only the Mac systems are observed); the larger systems have a near 1:1M :C ratio and are described as metalkarbon nanocrystals.Ti,,CT3 has a 3 x 3 x 3fcc sodium chloride-like struc- ture. Other fcc clusters suggested are Ti,,CT9 Ti,,C,f, Ti23C15 Ti2,C17 Ti3,C,+,,Ti3 'Ci3 and Ti&,+ though substituted c6 and tube structures are also possibilities. S. F. Cartier Z. Y. Chen G.J. Walder C. R. Sleppy and A. W. Castleman Jr Science 1993 260 195. J. S. Pilgrim and M. A. Duncan J.Am. Cliem. SOC. 1993,115,4395; S. Wei B. C. Guo J. Purnell,S. A.Buzza and A.W. Castleman J. Phys. Chem. 1993 97 9559. R. W. Grimes and J. D. Gale J. Phys. Chem. 1993 97 4616. M.-M. Rohmer M. Benard C. Henriet C. Bo,and J.-M. Poblet J. Chem.SOC.,Chem. Commun. 1993; 1182; Z. Lin and M.B. Hall J. Am. Chem. SOC.1993 115 11 165. ' I.G. Dance Aust. J. Chem. 1993 46 727. B.C. Guo K. P. Kerns and A. W. Castleman Jr J. Am. Chem. Soc. 1993 115 7415. ' J. S. Pilgrim and M.A.Duncan J. Am. Chem. SOC. 1993 115,9724. 119 120 S. A. Cotton metal-metalbond is omitted from the structure for clarity (Reproduced with permission from J. Am. Chem. Soc. 1993 115 11 165) 3 Halides and Their Complexes Two theoretical studies of TiCl, ZrCl, and HfCl have been reported.,^^ The mechanism" of the TiC1,-assisted Passerini reaction for the synthesis of C-C bonds between ketones and isocyanides has been clarified. Octahedral [TiCl,(thf),] loses thf in dichloromethane to give dimeric [Ti2(p Cl),Cl,(thf),] which shows high activity for ethene polymerization.' ' [ZrF4(dmso)(H,O),]~2H,O has pentagonal coordination of zirconium as does dimeric [Zr,F,(dmso),].' Seven coordination this time with [ZrF,I3 -polyhedra is found' in [NaBaZrF,] but [LiBaZr,F '3 has' square antiprismatic ZrF coordina- tion in planar [Zr,F,,I8- units.[dienH,][M,Fll(H20)2] (M = Zr,Hf) has tet- rameric chain complex anions [M,F22(H20)2]6- ; [dienH,][MF,].H,O contains pentagonal bipyramidal [MF,] - whilst [dienH,][M,Flo]-H,O has a polymeric structure.' HfC1 reacts with FeC1 and MeCN affording [HfC1,(NCMe),][FeC14], which has a structure analogous to the corresponding Zr compound.'6 Ammonolysis of P-ZrF or ZrF,.NH gives ZrNF (ZrO structure) and Zr40N,F,.'7 The hafnium(m) compound [Hf,CI,(PEt,),] has octahedrally coordinated hafnium' with a similar structure to the Zr analogue; it successively exchanges phosphines with trimethylphosphine affording ultimately [Hf2C1,(PMe,),].cis-[TiCI,(SHR),] (R = cyclohexyl and cy~lopentyl'~) have been synthesized and the structure of the cyclohexylthiol complex determined; it affords TiS films under low-pressure chemical vapour deposition (CVD) conditions.' V. Subramanian M. Vijayakumar and T. Ramasami Inorg. Chem. 1993 32 357. V. Jonas G. Frenking and M.T. Reetz Organometallics 1993 12 21 11. lo T. Carofiglio P. G. Cozzi C. Floriani A. Chiesi-Villa and C. Rizzoli Organometallics 1993 12 2726. l1 P. Sobota J. Ejfler S. Szafert K. Szczegot and W. Sawka-Dobrowolska J. Chem. SOC.,Dalton Trans 1993 2353. l2 Y.Gao J. Guery and C. Jacoboni Acta Crystallogr. Sect.C Cryst. Struct. Commun. 1993 49 963. l3 Y. Gao J. Guery and C. Jacoboni Eur. J. Solid State Inorg. Chem. 1992 29 1285. '* Y. Gao J. Guery and C. Jacoboni Eur. J. Solid State Inorg. Chem. 1992 29 1243. l5 R. L. Davidovich V. B. Lagvinova and L. V. Teplukhina Koord. Khim. 1993 19 283. l6 B.I. Kharisov S.S. Berdonosov S. I. Troyanov and N. Gonzales Koord. Khim. 1992 18,933. l7 R. Schlichenmaier E.Schweda and J. Strahle Z. Anorg. Allg. Chem. 1993 619 367. '' M.E. Riehl S.R. Wilson and G. S. Girolami Inorg. Chem. 1993 32 218. l9 C.H. Winter T.S. Lewkebandara J. W. Proscia and A. L. Rheingold Inorg. Chem. 1993 32 3807. Ti,Zr and Hf 121 TiCl,-ester complexes have been studied to shed light on Ziegler-Natta processes; esters are used as internal donors in the catalyst preparation which characteristically involves titanium chloride on a MgC1 support with added ester.Tic, reacts with trimethyl 1,3,5-benzenetricarboxylate to give polymeric [Ti,Cl ,{ 1,3,5-C,H,(CO,Me),)] and [Ti2C~,{p-~,3,~-C6H3(C02Me)3}2];20a the ally1 acetate com- plex [{TiC13(p-C1),(MeC0,CH2CH = CH,)),] is also a dirner.,Ob In contrast seven diester complexes [TiCl,(diester)] are all monomeric with cis coordination of the ester.21 [TiMgC1,.4EtOAc] reacts with two moles of carboxylic acids to give [T~M~C~,~(O,CR),~~E~OAC].~~ Reduction of TiC1 or TiCl with Mg in thf gives first [TiMgCl,.xthfl then [Ti(MgCl),.xthfl on further reduction; the reaction is reversible in the presence of excess TiCl,. EXAFS studies, on [Ti(MgCl),.xthfl indicate a dimeric structure.Clusters attracting attention include the new zirconium iodide carbide phase Cs,Zr,I18C synthesized by reaction of CsI ZrI, Zr and C at 800 "C (but not 850 "C) which is isostructural with K,Zr71,,H.24 More examples of systems with this structure are M,M'Zr,Cl,,Z and MM'Zr,Cl,,Z (M = K-Cs; M' = Ca Ba La; Z = B C Mn and Fe); all are based on Zr6C11,Z units linked by countercations (2).,' 4 Oxides and Other Binary Compounds The optical properties of 'ultrafine' TiO (particle size 20 nm) leading to its use as a UV filter have been reviewed.26 TiO has received attention as a photo~atalyst~~ for metal-enhanced oxidation of organic materials in water. Methods of producing TiO aerogels and powders by alkoxide hydrolysis have been reported,28 whilst proton exchange and dehydration below 350 "C of layered titanates gives29 metastable TiO,(B).ZrO is also a phot~catalyst~' whilst sol-gel-derived ZrO is a very active CO hydrogenation ~atalyst.~' Solution routes to perovskite-phase mixed-metal oxides have been reviewed., Microwave synthesis of the hard refractory TIN from anhydrous TiC1 and Li,N has been attained,, another route being CVD from a TiC1,-NH,-H system., Another CVD route uses [Ti(N,),Cp,] as the starting material for either thermal or 'O (a)P. Sobota J. Utko and T. Lis J. Organomet. Chem. 1993,447,213; (b) T. Lis J. Utko and P. Sobota Acta Crystallogr. Sect. C Cryst. Struct. Commun. 1993 49 2089. " H. J. Kakkonen J. Pursianen T.A. Pakkanen M. Ahlgren and E. Iiskola J.Organomet. Chem. 1993,453 175. '' D.A. Brown and M.G. H. Wallbridge Inorg. Chim. Acta 1993 206 209. 23 L. E. Aleandri B. Bogdanovic A. Gaides D. J. Jones S. Liao A. Michalowicz J. Roziere and A. Schott J. Organomet. Chem. 1993 459 87. 24 W. Payne and J. D. Corbett J. Solid State Chem. 1993 102 553. " J. Zhang and J.D. Corbett Inorg. Chem. 1993 32 1566. 26 V.P. S. Judin Chem. Br. 1993 503. 27 A. Wold Chem. Mater. 1993 5 280; J. Papp H-S. Shen R. Kershaw K. Dwight and A. Wold Chem. Mater. 1993 5 284. '* L. K. Campbell B. K. Na and E.I. KO,Chem. Mater. 1993,5 1329; G. W. Koebrugge L. Winnubst and A.J. Burggraaf J. Mater. Chem. 1993 3 1095. 29 T. P. Feist and P. K. Davies J. Solid State Chem. 1992 101 275. 30 K. M. Ganguly S. Sarkar and S. N. Rhattacharyya J.Chem. SOC. Chem. Commun. 1992 682. 31 Y. Sun and P.A. Sermon J. Chem. Soc. Chem. Commun. 1992 1242. 32 C. D. Chandler C. Roger and M. J. Hampden-Smith Chem. Rev. 1993 93 1205. 33 J. C. Fitzmaurice A. Hector and I. P. Parkin Polyhedron. 1993 12 1295 34 C.-C. Jiang T. Goto and T. Hirai J. Alloys Comp. 1993 190 197. 122 S. A. Cotton (Reproduced with permission from Inorg. Chem. 1993 32,1566) photoassisted CVD.35 Mixtures of TiCl and Li3N or TiCl and Li,O react on either thermal or frictional initiation to give TIN and TiO re~pectively.~~ TiB,-TiN nanocomposites have been studied3' whilst films of TiS, a potential cathode material for lithium batterie~,~~ have been made by CVD. 5 Alkoxides Amides and Imides [Zr(OBu),] has been used as the starting material in the synthesis of some eight-coordinate bis(disalicy1idene- 1,2-diaminocyclohexane) complexes.39 Deposition of [Zr(OR),] (R = t-butyl neopentyl) onto an Al,03 surface demonstrates a significant hydrogen isotope effect.,' Partial hydrolysis of [{ LiTi(oP~-')~},l gives a tetramer [{ LiTiO(OPr'),),] (3) which has a structure related to ferroelectric titanates;,l [BaZr,(OPr') 8] gives 35 K. Ikeda M. Maeda and Y. Arita Japan J. Appl. Phys. Part I. 1993,32 3085 (Chem. Abstr. 1993 119 170301). 36 A. Hector and I. P. Parkin J. Chem. SOC.,Chem. Commun. 1993 1095. 37 K. Su M. Nowakowski D. Bonnell and L.G. Sneddon Chern. Mater. 1991,4 1139. 38 C. H. Winter T. S. Lewkebandara and J. W. Proscia Chem. Mater. 1991 4 1144. 39 M.L. Illingworth B. P. Cleary A. J. Jensen L. J. Schwartz and A. L. Rheingold Inorg. Chim. Acta. 1993 207 147. 40 J. B. Miller and J. Schwartz Acta Chem. Scand. 1993 47 292. 41 R. Kuhlman B. A. Vaartstra W. E. Streib J. C. Huffmann and K. G. Caulton Inorg. Chem. 1993,32,1272. 123 Ti,Zr and Hf 0= isopropoxide,0= oxide (Reproduced with permission from Inorg. Chem. 1993 32 1272) [BaZr,(OH)(OPr') ,] on hydrolysis. Anhydrous gadolinium acetate reacts with [{Zr(OPr'),(Pr'OH)},] to give [Gd,Zr4(p4-O)(p-OAc)6(p-OPri)lo(OPr~)lo], which has two GdZr,(p4-O)(p-OAc),(OPr~)lo tetrahedral clusters associated by acetate bridges4 [M(OPr'),] (M = Ti Zr) react with acrylic acid to form [M(OPr'),(O,CCH=CH,)] which combines with PHPh to give the phosphino- spacer substituted alkoxide [M(OPr'),(O,CCH,CH,PPh,)]; [Zr(OPr'),-(O,CCH,PPh,)] can be made from [Zr(OPr'),(O,CCH,Cl)] and LiPPh,.43 [TiCl,(OAr),] (Ar = 2,6-Ph,C,H4) catalyses the formation of cycl~hexadienes.~~ Ab initio calculations on small molecule elimination by Group 4amides have been4' carried out in the context of CVD precursor design.Polyfunctional amide ligands have been used to synthesize titanium amide halide complexes.46 The rates of substitution in a series of (dialky1amido)titanatranes (4) (X = NMe, NEt, NPr,) have been studied,47 and a range of new derivatives synthesized (X = OAr SAr etc.). TiCl reacts with N(SiMe,) to form the imide [{TiCI,{N(SiMe,)}},] which has a ring structure with two different titanium environments; this reacts with [PPh,]CI to give dimeri~~~ [PPh,],[{TiCl,(N(SiMe,)}},] with five-coordinate titanium linked by imide bridges (5).In contrast [PPh4],[{TiCl,(OSPC12)}2]has two chlorine bridges.49 51me3 1 SiMe (4) (5) 42 S. Daniele L. G. Hubert-Pfalzgraf J.-C. Darn and R. A. Toscano Polyhedron. 1993 12 2091. 43 H. Buhler and U. Schubert Chem. Ber. 1993 126 405. 44 G.J. Balaich and I. P. Rothwell J. Ant. Chem. Soc. 1993,115 1581; J. E. Hill G. J. Balaich P. E. Fanwick and I. P. Rothwell Organometallics 1993 12 291 1. 45 T. R. Cundari and M. S. Gordon J. Am. Chem. SOC. 1993 115 4210. 46 S. Friedrich L. H. Gade A. J. Edwards and M. McPartlin J. Chem. SOC. Dalton Trans. 1993,2861; Chem. Ber. 1993 126 1797. 41 A. A. Nanini S. L. Ringrose Y.Su R. A. Jacobson and J.G. Verkade Znorg. Chem. 1993 32 1290. 48 R. Schlichenmaier and J. Strahle Z. Anorg. Allg. Chem. 1993 619 1526. 49 R. Wollert S. Wocadlo K. Dehnicke H. Goesmann and D. Fenske 2.Natuiforsch. B Chem Sci. 1992,47 1386. 124 S. A. Cotton A wide range of Group 4 aryl imides has been made,50 such as [M(OAr),(NHPh),] (e.g. OAr = OC,H3-2,6-Pr:) [M(NHAr),] and [M(OAr),(NPh)(py),]; the four- coordinate compounds are tetrahedral and the five-coordinate compounds distorted trigonal bipyramidal. Several titanium(1rr) benzamidinates have been ~ynthesized.~ 6 Complexes of Macrocycles The crown ether complex [TiCl,(NCMe)( 15-crown-5)][SbC16] has octahedral coor- dination of titanium with a bidentate crown ether.52 [TiCl,(Me,tacn)] reacts with Naacac in methanol in the presence of air to give tetranuclear [{Ti(OMe)(Me,tacn)} ,(p-O){Ti(acac),} ,][CIO,] (6).53 n A general preparative route for titanium@) tetratolylporphyrin complexes [Ti(RC=CR)(ttp)] has been reported.The coordinated alkyne can be displaced by pyridines; the structure of [Ti(Lt-picoline) (ttp)] has been determined.54 The complexes [Ti(X,)(oep)] (X = 0 S Se) participate in transfer reactions involving 0,S and Se.” [TiO(pc)] is a highly photoactive molecular semiconductor. Photochemical cleavage of the peroxide link in [Ti(O,)(tpp)] gives [TiO(tppo)lS6 (tppo = tetraphenylporphyrin N-oxide) which reacts quantitatively with triphenyl- phosphine to yield [TiO(tpp)] .57 Oxidation of the titanium(1v) phthalocyanine [Ti(pc),] with iodine and nitric acid5* gives [T~(PC),][I,]~/~ and [Ti(pc),]NO,; the former has non-integrally charged [Ti(pc),] 2/3 ions and the phthalocyanines are no + longer ‘stapled’ together.C. H. Zambrano R.D. Profilet J. E. Hill P. E. Fanwick and I.P. Rothwell Polyhedron. 1993 12 689. ” D.G. Dick R. Duchateau J. J. H. Edema and S. Gambarotta Inorg. Chem. 1993 32 1959. 52 M. Plate G. Frenzen and K. Dehnicke 2. Naturforsch. B Chem. Sci. 1993 48 149. ” P. Jeske K. Wieghardt and B. Nuber 2. Naturforsch. B Chem. Sci.,1992 47 1621. 54 L. K. Woo J. A. Hays V. G. Young C. L. Day C. Caron F. D’Souza and K. M. Kadish Inorg. Chem. 1993 32,4186. ’’ L.K. Woo and J.A. Hays Inorg. Chem. 1993 32 2228. 56 M. Hoshino K. Yamamoto J. P. Lillis T. Chijimatsu and J.Uzawa Inorg. Chem. 1993 32 5002. ” P. Ghosez R. Cbte L. Gastonguay G. Veilleux G. Dents and J. P. Dodelet Chem. Muter. 1993,5 1581. ’’ A. Capobianchi C. Ercolani A. M. Paoletti G. Penessi G. Rossi A. Chiesi-Villa and C. Rizzoli Inorg. Chem. 1993 32 4605. Ti Zr and Hf The syntheses are reported of [ZrCl,(oep)] [ZrCl,(tpp)] and [ZrCl,(tpp) (thf)],' the last having seven-coordinate zirconium. [ZrCl,(porphyrin)] are start- ing materials for the synthesis of [Zr(C,B,H l)(oep)] and [Zr(Me),(tpp)].60 [ZrCl,(oep)] is also a convenient starting material for a wide range of coordinative- ly unsaturated complexes [ZrR,(oep)] (R = alkyl aryl OR OAc triflate; R = cot) which undergo ready protonolysis hydrogenolysis and insertion of acetone and CO into the Zr-C bonds;61 structures reported for R = Me C1 and OCMe confirm cis ligation.[HfCl,(H,O)(oep)] is seven-coordinate60 as is [NBu,] [Hf(oep)(P,O,)]. EPR spectra of cation radicals generated from zirco- nium(Ivb(oep) complexes have been studied; [Zr(acac),(oep)] reacts with bromine forming [Zr(3-Bracac),(oep)] .62 The zirconium octaethylporphyrinogen complex [Zr(thf)(q5,q1,q5,q1-Et,N,)] (7) has been studied6 as a carrier for sodium hydride in toluene that will then insert alkenes or alkynes into the Zr-H bond. Calculations indicate that the a-bonding mode is dominant for the porphyrinogen ligand in zirconium complexes.64 7 Borohydrides Ab initio UHF calculations on [Ti(BH,),] indicate that a C, structure with q3 ligands6' is the most stable in keeping with experimental data (see Annual Reports Section A 1991 p.102); in contrast q2,q2,q3 bonding is predicted for [Ti(BH4),(PH3),] whereas experiment suggests the q1,q2,q3 mode. In the bis(imine) complexes [M(BH,),(Bu'NCH=CHNBu')l (M = Ti Zr) the zirconium complex has q3,q3 borohydride coordination but the titanium compound is q2,q3 bound.66 [Ti(BH,) effects anti-Markovnikov hydration of alkene~.~~ 59 H.-J. Kim D. Whang K. Kim and Y.Do Inorg. Chem. 1993,32 360. S. Ryu D. Whang J. Kim W. Yeo and K. Kim J. Chem. SOC. Dalton Truns. 1993 205. 61 H. Brand and J. Arnold Organometallics 1993 12 3655. 62 J. W. Buchler M. Eberle P. Hammerschmitt J. Huttermann and R. Kappl Chem. Ber. 1993 126,2619. 63 D. Jacoby C. Floriani A. Chiesi-Villa and C.Rizzoli J. Am. Chem. SOC. 1993. 115 3595. 64 A. Rosa G. Ricciardi M. Rosi A. Sgarnellotti and C. Floriani J. Chem. SOC. Dulton Trans. 1993 3759. '' A. Jarid A. Lledos Y. Jean and F. Volatron Inorg. Chem. 1993,32 4695; F. Volatron M. Duran A. Lledos and Y. Jean Inorg. Chem. 1993 32 951. 66 W.A. Herrmann M. Denk W. Scherer and F.-R. Klingan J. Organomet. Chem. 1993 444,C21. " K. S. Ravi Kumar S. Baskaran and S. Chandrasekaran Tetrahedron Lett. 1993 34 171. 126 S. A. Cotton 8 Other Complexes Titanium(II1) has been used in the assay of bacterial luminase.68 NMR studies of the classic tetrameric zirconium aqua ion [Zr,(OH),(H,0),,]8 indicate6’ two labile and + two strongly bound waters per zirconium. Syntheses have been reported of [TiL,] [ZnX,]X (L = N-methylurea N,N’-dimethylurea) and the structure of [Ti(N-meth ylurea),] [ZnCI,] C1 determined.Among eight-coordinate species the kinetics of the ligand exchange7 ’ between [Hf(acac),] and Hacac and some bis(tetradentate) zirconium(1v) complexes have been studied by variable-temperature NMR spectroscopy. Structures have been reported for the racemic [Zr(trans-dsd),] and [Zr(S,S-trans-dsd),] (trans-dsdH = N,N-dis-alicylidene-trans- 1,2-diaminocyclo hexane). Barium titanyl ~xalate,~ Ba[TiO(C,O,),]~SH,O is a molecular precursor for BaTiO (widely used in high dielectric ceramics for capacitors) with six-coordinate titanium(1v). [NH4][Ti(C,O,),].2H,O has a structure containing eight-coordinate titanium73 whilst in Na[Ti(H2O)(edta)].2H,O the titanium is seven-coordinate (pentagonal bipyramidal c~ordination).~~ Seven coordination is alsofound7 in dimeric [{Ti(thped)},][thped = N,N,N’,N’-tetrakis-(2-hydroxypropyl)ethylenediamine].Some zirconium phosphate phosphonates ZrPO,(H,PO,) -x(RP0,0H),~xH20 have been synthesized by replacing the interlayer dihydrogen phosphate groups in y-ZrPO,(H2PO,).2H,O; interlayer distances were determined as a preliminary to inter~alation.~, Zirconium monophenyldiphosphonate phosphates have been syn- thesized as potential ion-exchange materials in nuclear waste effluent treatment. 77 Hydrothermal reactions of NaZr (PO,) and sodium silicate yield sodium zirconium silicoph~sphates.~~ A simple” route to amide-functionalized zirconium carboxyethyl- phosphonates has been described.The synthesis of titanium phosphate gels by reaction of phosphoric acid esters with titanium alkoxides and their use in the thin-film synthesis of potassium titanyl phosphate has been e~plored.~’ Coupled substitution of niobium and silicon in KTiOPO and KTiOAsO leads to new non-linear optical materials KTi,-,Nb,OX,-,Si,O (X = P As),81 with x up to 0.4. The structures of TiOS0,-xH,O (x = 0 1) have been reported.82 68 R.A. Jewsbury and J. Zeng J. Chem. Soc. Chem. Commun. 1993 1677. 69 M. Aberg and J. Glaser Inorg. Chim. Acta. 1993 206 53. 70 A. Kamkar T.J. King and J.P. Day Amirkabir 1992 5 69 (Chem. Abstr. 1993 119 216 143). 71 W.-S. Jung T. Nakagawa and H. Tomiyasu Inorg. Chim. Acta. 1993 209 79. 72 W.E. Rhine R. B. Hallock W.M. Davis and W. Wong-Ng Chem. Mater. 1992 4 1208. 73 R.B. English and D. J. Eve Inorg. Chim. Acta. 1993 203 219. 74 T. Mizuta J. Wang and K. Miyoshi Inorg. Chim. Acta. 1993 203 249. 75 D.F. Evans J. Parr S. Rahman A.M.Z. Slawin D.J. Williams C.Y. Wong and J.D. Woollins Polyhedron. 1993 12 337. 76 G. Alberti M. Casciola R.Vivani and R. K. Biswas Inorg. Chem. 1993 32 4601. 77 Chem. Abstr. 1993 119 126791. 78 Y. Yue and W. Pang J. Mater. Sci. 1993 28 1839. 79 T. Kijima Y. Kawagoe K. Mihara and M. Machida J. Chem. Soc. Dalton Trans. 1993 3827. C. Schmutz E. Basset P. Barboux and J. Maquet J. Muter. Chem. 1993 3 393. K. K. Rangan B. R. Prasad C. K. Subramanian and J. Gopalakrishnan Inorg. Chem. 1993 32 4291. 82 B. M. Gatehouse S. N. Platts and T. B. Williams Acta Crystallogr.Sect. C Cryst. Struct. Cornmun. 1993 49 428. 127 Ti,Zr and Hf 9 Organometallics A review has appeared of the use of zirconocene derivatives,' whilst chiral monocyclopentadienyl compounds mediate stereoselective transformation^.'^ [TiBr,Cp,] has the expected pseudotetrahedral structure with two q5-ligands,85as have [Z~C~,(C,H,BU~),],'~ [ZrC1,(C,Me,Et),],87 and [TiCl,Cp;]; the structures of [TiClCp;] [TiICp;]," and [ZrF,(C,H3(SiMe,),)(C5H4(SiMe3)}]''are also bent sandwiches. Redox reaction of [Ti(AICI,),(C,H,)] with corresponding cyclopen- tadienes gives [Ti(AlCl,),(C,R,)] (R = Bz H)" with bidentate tetrachloroalumi- nates. [TiCl,Cp*] reacts with excess AsF to form'' [TiC13Cp*],.2AsF3 where the weakly held AsF molecules are removeable in uucuo whilst [MCl,Cp] (M = Zr Hf) react with [Li(Me,C(C,Me,),}] to form [MC1Cp(Me2C(C,Me4),}] the hafnium compoundg2 being the first tris(q5-cyclopentadienyl)of this metal.A complex of the cis-1,3,5-cyclo hexanetrialkoxide ligand [Ti (C ,H (SiMe,),} (0,C6H9)] (8) has an adaman tane-li ke structure. [TiCI,Cp*] reacts with AlMe to form [TiCI,MeCp*] which in turn undergoes insertion reactions with molecules like CO and isocyanides; the structure of [TiC12(q2-COMe)Cp*] was determined.94 [TiCl,Cp,] and related compounds react with Grignard reagents to form systems that have long been studied by EPR; crystalline solids isolated from these systems include the dimeric [{Ti(,u-H),(C,Me,H),Mg(,u-X)(OEt,} J (X = C1 Br) and C(T~(,~-H),CP~},M~I.~~ [TiCl,Cp,] reacts with potassium enolatesg6 to give enolate complexes whose 83 R.D. Broene and S. L. Buchwald Science 1993 261 1697. 84 R.O. Duthaler A. Hafner P. L. Alsters P. Rothe-Streit and G. Rihs Pure Appl. Chem. 1993,64 1897. 85 N. Klouras V. Nastopoulos I. Demakopoulos and I. Leban Z. Anorg. Allg. Chem. 1993 619 1927. 86 U. Bohme and H. Langhof Z. Kristallogr. 1993 206 281. S. Kiirz and E. Hay-Hawkins Z. Kristallogr. 1993 205 61. 88 S.I. Troyanov V. B. Rybakov U. Thewelt V. Varga and K. Mach J. Organomet. Chem. 1993,447,221. 89 C. H. Winter T. S. Lewkebandara X. Shui and X.-X. Zhou J. Cryst. Spectroscopic Res. 1993 23,685. 90 G. Schmid U. Thewelt S.I. Troyanov and K. Mach J. Organomet. Chem. 1993,453 185. 91 M. Sotoodeh I. Leichtweis H.W. Roesky M. Noltemeyer and H.-G. Schmidt Chem. Ber. 1993,126,913. 92 G.M. Diamond M. L. H. Green,N. A. Popham,and N. Chernega J.Chem.Soc.,Dalton Trans. 1993,2535. 93 D. M. Choquette W. E. Buschmann M. M.Olmstead and R. P. Planalp Inorg. Chem. 1993 32 1062. 94 A. Martin M. Mena M. A. Pellinghelli P. Royo R. Serrano and A. Tiripicchio J. Chem. Soc. Dalton Trans. 1993 2117. 95 S.I. Troyanov V. Varga and K. Mach J.Organomet. Chem. 1993,461,85;J.Chem. SOC. Chem. Commun. 1993 1174. 96 P. Veya C. Floriani A. Chiesi-Villa and C. Rizzoli Organometallics 1993 12 4892. 128 s. A. Cotton reactivities have been explored. Synthesis of dimeric zirconium q2-aldehyde complexes such as [{Zr(q2-OCHCH,CHMe,)Cp,},] has been achieved.97 The benzene solvate of [{ZrOCp,),] is trimeric,'* with a planar Zr,O core and short Zr-0 bonds indicative of partial double bonding.[Ti(q-C,H,)Cp;] reacts with N,O in py-thf forming monomeric [Tipy (O)CpT] which on warming affords tetranuclear [Ti,(p- o)6cp*].99 [TiF,Cp*] reacts with O(SnBu,), thus giving the eight-membered ring compound [{Ti@-O)FCp*),].' O0 [TiCl,Cp] reacts with propane- 1,3-dithiol to give [TiCl(SCH,CH,CH,S)Cp] replacement of the chloride giving' O' [TiPh(SCH,CH,CH,S)Cp] and [TiPh,(SCH,CH,CH,S)Cp] -. Two isomers of [TiCl(dmpe)(SCH,CH,CH,S)Cp] one with chelating dmpe and the other with a monodentate phosphine were reported. A series of phosphides and phosphinidines has been synthesized; [ZrCl,Cp:] reacts with LiPHPh to form [Zr(PHPh),Cp;] which on standing affords [Zr(PPh,)Cp;] then [Zr(PPh),Cp;].lo2 The remarkable salt of a dimeric zirconium anion [Li2(p-N2)(thf)6][{zr(p-PPh)Cp},] (9) gives a triplet EPR spectrum as an S = 1 bis(Zr"') species.'03 Other Zr-P bonds have been formed by oxidative addition of P-H bonds to zirconocene.' O4 The structure of [Zr(PPh,),(C,H,SiMe,),] has been described;" this has been converted into the heterobimetallic hydroformylation catalyst [Zr(p-PPh,),(C,H,SiMe,),Rh(p-SBu')2Rh(~-PPh,)2Zr(C~H4SiMe3)2].Both C-C and P-C coupling reactions take place when [TiCl,Cp,] reacts with LiCH,PMe and Li{CH(PMe,)(SiMe,),} to give the complexes [Ti(Me,PCH,CH,PMe,)Cp,] and Me,SiCH,PMe,=C(PMe,)SiMe, respectively.'06 A p-dihydro ansa-metallocene [Zr,(p-H),Cl (q5,q3-C ,H,C(Me) (fluorenyl)) ,]has been O7 characterized.97 F. R. Askham K. M. Carroll S. J. Alexander A. L. Rheingold and B. S. Haggarty Organometallics. 1993 12 4810. 98 0.A. Mikhailova M. H. Minacheva V. B. Burlakov V. B. Shur A. P. Pisarevsky A. I. Yanovsky and Yu. T. Struchkov Acta Crystallogr. Sect. C. Cryst. Struct. Commun. 1993 49 1345. 99 M.R. Smith P.T. Matsunaga and R.A. Andersen J. Am. Chem. Soc. 1993 115 7049. loo H. W. Roesky I. Leichtweis and M. Noltemeyer Inorg. Chem. 1993 32 5102. T.T. Nadasi Y. Huang and D. W. Stephan Inorg. Chem. 1993 32 347. lo' Z. Hou T. L. Breen and D. W. Stephan Organometallics 1993 12 3158. '03 J. Ho R. J. Drake and D. W. Stephan J. Am. Chem. SOC.,1993 115 3792. lo4 J. Ho Z. Hou R. J. Drake and D. W. Stephan Organometallics 1993 12 3145. lo' A.-M.Larsonneur R. Choukroun J.-C.Daran,T. Cuenca J. C. Flores and P. Royo J. Orgunornet. Chem. 1993 444,83. lo6 H. H. Karsch B. Deubelly G. Grauvogl and G. Muller J. Organomet. Chem. 1993 459 95. M. Bochrnann S. J. Lancaster M. B. Hursthouse and M. Mazid Organometallics 1993 12 4718. Ti,Zr and Hf Fulvalenes continue to attract interest. In [Ti,R,(p-C,,H,)Cp,] (R = Me'" and Ph'09) the fragments are on opposite sides of the fulvalene bridge. Titanocene reacts with HC1 or Br then LiMe and hydrolysis of the product gives the fulvalene-bridged compounds [TiX,(p-O)(p-Cl,H,)cp2] (X = Cp or Br);"' the chloro complex (10) has also been made' "by reaction of the fulvalene titanium(II1) hydride [Ti(p-H),(p- C,,H,)Cp,] with chlorine to give [Ti,(p-C~),(p-CloH,)Cp,l,followed by reaction with azobenzene in wet toluene.The study of benzyl complexes (benzyls are more stable than methyls) particularly cationic species such as [M(CH2Ph)Cp2]+ is prompted by their role as the catalytically active moiety in the polymerization of a-alkenes by the Ziegler-Natta process. Comparison' l2 of the structures of [Ti(CH,Ph),Cp] and [Ti(CH,Ph),Cp,] indicates that the benzyl ligands in the latter tend towards a dihapto mode of coordination. The structure of [Zr(CH,Ph),(C,H,SiMe,),] has also been deter- mined.'' Tetrabenzylzirconium reacts with B(C,F,) to give the unusual Zwitterionic c~mpound"~ [Zr(CH,Ph),][B(CH,Ph)(C,F,),I in which the zirconium is bound to the two monohapto benzyls one dihapto benzyl and the anion in an q6 fashion.[M(CH,Ph)Cp,] and' '' related base-free cationic species containing q2-bound + benzyls are active polymerization catalysts (significantly better than the corresponding methyls) at ambient pressure. The single propene insertion product [Zr(CH,CHMeCH,Ph)(CH2Phz~][B(CH2Ph)(C6F5)3] has been isolated.' l6 Similar n-coordination is found' ' in the complex [Zr(CH,Ph),Cp][B(CH,Ph)(C,F,),I. [Zr(CH,Ph),Cp,] reacts with Ag[CB ,H,,] forming [Zr(CH,Ph)(q'-CB lHl,)Cp,] 'l8 (methyls have also been investigated) whilst [Ti(CH,Ph)(q'-CB ,H,,)Cp,] has been observed spectroscopically in a study' l9 of the oxidation and protolysis chemistry T. Wohrle and U. Thewalt J. Organomet. Chem. 1993 456 C21. T. Wohrle and U. Thewalt Z. Naturforsch. B Chem.Sci. 1993 48 603. 'Io T. Wohrle and U. Thewalt J. Organomet. Chem. 1993 447 45. 'I1 A. Cano T. Cuenca,G. Rodriguez P. Royo C. Cardin and D. J. Wilcock J. Organomet. Chem. 1993,447 51. 'Iz J. Scholz F. Rehbaum K.-H. Thiele R.Goddard P. Betz and K. Kriiger J. Organomet. Chem. 1993,443 93. 'I3 K.-H. Thiele U. Bohme and J. Sieler Z. Anorg. Allg. Chem. 1993 619 1951. 'I4 C. Pellecchia A. Grassi and A. Immirzi J. Am. Chem. SOC. 1993 115 1160. 'Is C. Pellecchia A. Immirzi A. Grassi and A. Zambelli Organometallics 1993 12 4473. 'I6 C. Pellecchia A. Grassi and A. Zambelli J. Chem. Soc. Chem. Commun. 1993 947. 'I7 M. Bochmann and S.J. Lancaster Oryanometallics 1993 12 633. 'I8 D.J. Crowther S. L. Borkowsky D. Swenson T. Y. Meyer and R. F. Jordan Organometallics 1993 12 2897.S. L. Borkowsky N.C. Baenziger and R. F. Jordan Organometallics 1993 12,487. 130 S. A. Cotton of [Ti(CH,Ph),Cp,]. [ZrCl,{q-RC(Ph)R)Cp,] acts',' as a cocatalyst for ethene and propene polymerization. Ab initio calculations indicate that agostic interactions play a role in stabilizing intermediates in the Ziegler-Natta process. ' ' Low-temperature (120K) photolysis of matrices of [Ti(CO),Cp,] gives [Ti(CO)Cp,] whilst photolysis of [Ti(N,),Cp,] in CO-doped matrices gives [Ti(CO),Cp,] [Ti(CO)Cp,] [Ti(NCO),Cp,] and [Ti(N,)2Cp,].'22 Reaction of [MCl,(thf),] (M = Zr Hf) with excess potassium 2,4-dimethylpentadienylide and PEt gives', [M(PEt3)(q5-2,4-C7H1 1)2]; other phosphine derivatives are similarly prepared. Exposure of the zirconium complexes to CO gives [Zr(CO),(q5-2,4-CHll),] (n = 1,2) with an unsymmetric orientation of the two pentadienyl ligands.Significant advances in the area of zerovalent carbonyl chemistry have taken place with the synthesis of the 18-electron [Ti(SnR,)(CO),]- (R = Me Ph CY),',~ [M(CO),(tacn)] (M = Ti Zr Hf) and [M(CO),(Me,tacn)] (M = Ti Zr),'25 the last evidently having 4 3 piano-stool structures. Carbonyl hydrides involving Cp as a coligand have also been examined.' 26 Unusual arene complexes'27 of these metals in the +4 oxidation state [MMe,Cp*(q6-arene] (M = Ti Zr Hf; arene = benzene toluene mesitylene styrene) have been reported as have divalent q-arene(bis-q-allyl) complexes of zirconium and hafnium.'28 [Ti(SnMe,),(q4-CloH8)2]2-is the first i~olated'~' bis(naphtha1ene) titanium complex.Monomeric zirconium(II1) organometallics are rare; further addi- tions to the ranks are provided by' 30 paramagnetic [ZrCl,(N(SiMe,CH,PPr,),}Cp] and its alkyl hydride and borohydride derivatives. Among studies of other zirco- nium(u1) systems Hartree-Fock calculations on dimers [{Zr(p-X)Cp,),] (X = I NH and PPh,) indicate a Zr-Zr bond for X = 1 and PPh,.I3l Reduction of [{Zr(p- H)(C,H,SiMe,),),] gives', [ZrH,(C,H,SiMe,),] -,characterized by EPR spectros- copy. A systematic study of the luminescence of charge-transfer states in titanium(1v) metallocenes has appeared. 33 120 A.N. Chernega R. Gomez and M. L. H. Green J. Chem. SOC. Chem. Commun. 1993 1415. R. Gleiter I. Hyla-Kryspin S. Niu and G. Erker Organometallics 1993 12 3828."' M. Tacke C. Klein D. J. Stufkens and A. Oskam J. Organomet. Chem. 1993 444,75. T. E. Waldman L. Stahl D. R. Wilson A.M. Arif J. P. Hutchinson and R. D. Ernst Organornetallics 1993 12 1543. lZ4 J.E. Ellis and P. Yuen Inorg. Chem.. 1993,32 4998. ''' J.E. Ellis A.J. DiMaio A.L. Rheingold and B. S. Haggarty J. Am. Chem. Soc. 1992 114 10677. lZ6 J. E. Ellis B. K. Stein and S. R. Frerichs .I.Am. Chem. SOC. 1993 115 4066. D.J. Gillis M.-J. Tudoret and M.C Baird J. Am. Chem. SOC. 1993 115 2543. M. L. H. Green and X. Morise J. Organomet. Chem. 1993 462 209. lZ9 J. E. Ellis D. W. Blackburn P. Yuen and M. Jang J. Am. Chem. SOC. 1993 115 11 616. 130 M. D. Fryzuk M. Mylvaganam M. J. Zaworotko and L. R. MacGillivray J. Am.Chem. SOC.,1993,115 10 360. R.L. DeKock M.A. Peterson L.E.L. Reynolds L.H. Chen E.J. Baerends and P. Vernooijs Organometallics 1993 12 2794. 13' A.-M. Larsonneur R. Choukroun and J. Jaud Organornetallics 1993 12 3216. 133 J. W. Kenney D. R. Boone D. R. Striplin Y.-H. Chen and K. B. Hamar Organometallics 1993.12,3671.

ISSN:0260-1818    

DOI:10.1039/IC9939000119

出版商:RSC    

年代:1993

数据来源: RSC