The Typical Elements By D. W. A. SHARP Department of Chemistry University of Gfasgow G12 800 M. G. H. WALLBRIDGE Department of Molecular Sciences University of Warwick Coventry CV4 7AL and J. H. HOLLOWAY Department of Chemistry University of Leicester Leicester LEI 7RH PART I Groups 1-111 1 Group1 Reduction of mixtures of metal oxides or fluorides (e.g. Li,O) and noble metals with very pure hydrogen gives intermetallic compounds which on heating in a high vacuum give the pure metal. By using noble metals as ‘catalysts’ Li Ca Sr, Ba Am and Cf may be obtained by hydrogen reduction.’ Two intermetallic structures of stoicheiometry A,B are now known Na,T1 has a complex arrange-ment of atoms comprising icosahedra and pentagonal prisms; there are no TI-TI contacts2 Lithium atoms produced at 1100-1300 K react with chloro-carbons to give polylithioalkanes e.g.CLi ;3a although monolithium derivatives of nitriles e.g. LiCH,CN are not formally electron-deficient compounds they are associated presumably by co-ordination from the nitrile Lithium halides associate with polymeric lithium alkyls in ethers and species such as Li,Me3Br are f~rmed.~‘ Nonafluorobicyclo[2,2,l]hept-2-en- 1-yl-lithium ( 1) and the Grignard derivative are relatively stable in diethyl ether and do not readily undergo /?-fluorine e l i m i n a t i ~ n . ~ ~ $,; F2 F (1) U. Berndt B. Erdmann and C. Keller Angew. Chem. Internut. Edn. 1972 11 515. S. Samson and D. A. Hansen A m Cryst. 1972 B28 930. ( a ) C. Chung and R. J. Lagow J.C.S. Chem. Comm. 1972 1078; ( b ) R.Das and C. A. Wilkie J . Amer. Chem. Soc. 1972 94 4555; (c) D. P. Novak and T. L. Brown ibid., p. 3793; (4 S. F. Campbell R. Stephens J. C. Tatlow and W. T. Westwood J . Fluorine Chem. 197112 1 439. 17 176 D. W. A . Sharp M . G. H . Wallbridge and J. H . Holloway Co-deposition of lithium atoms and nitrogen molecules produces species LIN, and N,Li,N,.4 A reinvestigation of the structure of lithium amide shows the crystal to have a distorted cubic close-packed arrangement of nitrogen atoms with lithium ions in the tetrahedral holes.'" Lithium dimethylamide LiNMe,, is best prepared from dimethylamine and butyl-lithium;5b it is a good reagent for introduction of the dimethylamino-group. The addition compound Li1,-3-ethylenediamine has the lithium in distorted octahedral co-ordination." A study of the effects of lithium halides on a-proton lineshapes of pyridine solutions has been interpreted in terms of such geometric models as linear Li+Cl-(py), linear Li+(H,O)(py) and tetrahedral Li+Cl-(~y)~ .5d The mechanisms of alkali-metal ion complex formation in solution have been reviewed ;6a amongst the methods used for studying alkali-metal complex formation are i.r.and n.m.r. spectroscopy (including 23Na spectroscopy)6b and the effect of alkali-metal ions on the N-C torsional barrier in amides.6' Pure lithium nitrite is prepared by interaction of lithium amide and ammonium nitrite in liquid ammonia. Amongst interesting structures of alkali-metal salts of oxyacids described recently may be mentioned KH(O,CCF,) which has a very short and apparently symmetrical hydrogen bond,8" and tetrameric trimethyl-phosphine oxide adducts of alkali-metal trimethylsilanoates which appear to have a cubane-type structure e.g.(2).8b Several apparently simple sodium salts R3Si ,0-PR, R~PO d 0 - K 4 K-0 I actually have the composition Na3M04(NaOH),-,~,5,12H,0 (M = P V or As) and contain sheets of composition Na(OH,) which have strong hydrogen bonds to the anionic groups present in the lattice.8c The 1,6dioxan (L) complexes NaC10,,3L NaBF4,3L and NaI,3L have the same structure as AgC104,3L with R. C. Spiker jun. L. Andrews and C. Trindle J. Amer. Chern. SOC. 1972 94 2401. ( a ) H. Jacobs and R. Juza Z . anorg. Chem. 1972,391 271 ; (b) S . Chan S. DiStefano, F. Fong H. Goldwhite P. Gysegen and E.Mazzola Synth. Inorg. Metal-org. Chem., 1972 2 13; (c) H. Gillier-Pandraud and S. Jamet-Delcroix Acta Cryst. 1971 B27, 2476; (d) D. W. Larsen J . Phys. Chem. 1972,76 53. ( a ) R. Winkler Structure and Bonding 1972 10 I ; (b) C. Lassigne and P. Baine J. Phys. Chem. 1971,75,3188; A. L. Van Geet J. Amer. Chem. SOC. 1972,94,5583; M. Herlem and A. I. Popov ibid. p. 1431; (c) W. Egan T. E. Bull and S. Forsen J.C.S. Chem. Comm. 1972 1099. ' P. Zecchini and C. Devin Compr. rend. 1972 274 C 524. * (a) A. L. MacDonald J. C. Speakman and D. HadZi J.C.S. Perkin 11 1972 825; (b) H. Schmidbaur and J. Adlkofer Chem. Ber. 1972 105 1956; (c) E. Tillmanns and W. H. Baur Acra Crysr. 1971 B27 2124 The Typical Elements 177 each metal ion octahedrally co-ordinated by oxygen ; the heavier alkali metals are too large to fit in this structure.' The chemistry of macrocyclic polyethers continues to be widely reported and has been reviewed,"" and a novel macro-tricyclic ligand (3) has been synthesized.lob The 2 1 complex between KNCS and 2,3 ;14,15-dibenzo-1,4,7,10,13,16,19,22-octaoxacyc1otetracosa-2,14-diene has the geometry (4) with close approach of an aromatic group to a potassium ion U Q and N-bridging thiocyanate groups.' OC The ligand dicyclohexyl- 18-crown-6 is in the cis-syn-cis-conformation in the isolated barium thiocyanate complex ; the J .C. Barnes and C. S. Duncan J.C.S. Dalton 1972 1732. l o ( a ) C. J. Pedersen and H. K. Frensdorf Angew. Chem. Internat. Edn. 1972,11 16; (6) J. Cheney J. M. Lehn J. P. Sauvage and M. E. Stubbs J.C.S.Chem. Comm. 1972, 1100; ( c ) D. E. Fenton M. Mercer N. S. Poonia and M. R. Truter ibid. p. 66; (4 N. K. Dalley D. E. Smith R. M. Izatt and J. J. Christensen ibid. p. 90; (e) R. M. Izatt, B. L. Haymore and J. J. Christensen ibid. p. 1308 ; (f) J. Cheney and J. M. Lehn ibid., p. 487; ( g ) D. J. Sam and H. E. Simmons J. Amer. Chem. SOC. 1972 94 4024; (h) F. Wudl J.C.S. Chem. Comm. 1972 1229 178 D. W. A . Sharp M . G. H . Wallbridge and J. H. Holloway nitrogen of the anions and a water molecule of hydration are co-ordinated to barium together with the six oxygens of the polyether.'Od The oxonium ion, H30+ may be complexed within a macrocyclic polyether,"' but if protons are located inside the molecular cavity they are very inactive and deprotonation is slow even in strong base.'OS It has been shown that potassium permanganate can be solubilized in benzene by use of a macrocyclic polyether thus providing a convenient and efficient oxidant.' Og A chiral ligand exhibits cation-dependent 0.r.d.curves which may be used to detect sodium in the presence of lithium or potassium. ' O h The alkali-metal methanethiolates MeSM have layer lattices the alkali-metal ions being four- (Li Na) or five- (K) co-ordinate." 2 Group11 Beryllium.-Although the structure of solid Be(BH,) is now known,"" the molecule is still of interest and there are apparently two isomers present in the vapour phase.'2b The complexes (RBeH),,L (R = Et Bus But or n-C,H ; L = NNN'N'-tetramethylethylenediamine) are all monomeric with a chelating ligand ;' 3a organoberyllium and organoberylliumhydride complexes have been reviewed.'3b At 173 K Cp,Be has one ring symmetrically n-bonded to the metal whilst the other ring is o-bonded in a 'slip' ~andwich;'~" both MeBeCp and CpBeCl appear from electron-diffraction studies to have symmetrically bonded Diarylberylliums can be formed in high yield by exchange between BeEt and triarylboranes; they form adducts with amines and ethers :' BeEt, reacts with NMe,SCN to form NMe,[(Et,Be),SCN] which is sulphur-bonded.'" Polymeric butoxyberyllium derivatives e.g. (ClBeOBu',L) (L = Et,O) and Me,Be,(OBu'), are formed from Be(OBu') and BeX ; SBu' and Me,N groups may also be substituted ;' 6a alkoxides derived from other tertiary alcohols are also polymeric.'6b The Be(NH,) - ion in KBe(NH,) is approximately planar with a relatively short Be-N bond which is consistent with some pn-pn bond-ing.' The structures of fluoroberyllates are now being determined.Salts MLiBeF (M = K NH, or Cs) have discrete BeF,'- tetrahedra"" whereas pentafluoroberyllates MBe,F (M = K NH, Rb T1 or Cs) have sheet anions, while one form of CsBe,F contains a complex arrangement of ten-membered rings of linked BeF tetrahedra.' 8b E. Weiss and U . Joergens Chem. Ber 1972 105 481. ( a ) D. W. A. Sharp M. G. H. Wallbridge and J. H. Holloway Ann. Reports 1971,68, A 256; ( 6 ) J . W. Nibier J . Amer. Chem. SOC. 1972 94 3349. l 3 ( a ) U. Blindheim G. E. Coates and R. C. Srivastava J.C.S. Dalton 1972 2302; ( 6 ) F. Bertin and G. Thomas Bull. SOC. chim. France 1971 3951.l 4 ( a ) C.-H. Wong T.-Y. Lee K.-J. Chao and S. Lee Acta Cryst. 1972 B28 1662; ( b ) D. A. Drew and A. Haaland J.C.S. Chem. Comm. 1971 1551. l 5 ( a ) G . E. Coates and R. C. Srivastava J.C.S. Dalton 1972 1541; (6) N. Atam H. Miiller and K. Dehnicke J . Organometallic Chem. 1972 37 15. ( a ) R. A. Andersen N . A. Bell and G. E. Coates J.C.S. Dalton 1972 577; ( 6 ) R . A. Andersen and G. E. Coates ibid. p. 2153. L. Guemas-Brisseau M. G . B. Drew and J. E. Goulter J.C.S. Chem. Comm. 1972, 916. ( a ) J . Le Roy and S. Aleonard Acfa Cryst. 1972 B28 1383; ( 6 ) Y . Le Fur ibid. p. 1 159; Y . Le Fur and S. Aleonard ibid. p. 21 15 The Typical Elements 1 79 Magnesium Calcium Strontium and Barium.-Both X-ray photoelectron and X-ray emission spectroscopy' may be used to determine co-ordination numbers in magnesium and aluminium compounds.Some properties of atomic magne-sium and calcium have been described Ground-state magnesium ('S) reacts with alkyl halides to give unsolvated Grignard reagents on warming; at 77K a black matrix in whch the magnesium appears to be weakly bonded to the halogen of the RX is obtained and these compounds have novel properties.20" Calcium atoms defluorinate unsaturated fluorocarbons e.g. CF3CF=CFCF, yields CF3CECCF,.20b A very active form of magnesium may be prepared by reducing the anhydrous halides with an alkali metal in an ethereal solvent.20c The existence of BaB has now been confirmed.2'" CaMgX and SrMgX (X = Si Ge Sn or Pb) have the ordered anti-PbC1 structure and are related to the binary compounds Ca,X whereas compounds BaMgX have the anti-PbFC1 structure.l b X-Ray crystallography confirms the presence of a symmetrical 7c-C5H5 group in CpMgBr,Et,N(CH,),NEt in the solid state.22 Many organomagnesium derivatives are associated in solution and two different bridges e.g. a methyl and an OCPh,Me are present in derivatives such as MeMgOCPh,Me., The action of hydrogen at high temperatures on strontium nitrides gives mixed nitride-hydrides e.g. Sr,N - .H ; these observations account for the previous records of non-stoicheiometry in these nitride^.,^" Ba,N forms a mixed silicide nitride BaSiN with Si,N .24b Calcium hydrazinecarboxylate has anions which both chelate one CaZf ion and bridge two such ions; co-ordination numbers about the metal are high zinc complexes have similar anionic arrangements but lower co-ordination numbers.Radical anions e.g. the anion of glyoxal-bis-(N-t-butylimine) form complexes with Mg2 + Ca2 + or Zn2 + which may be studied by e.s.r. spectroscopy;25b the Ca2+ ion shows a very specific interaction with the nucleoside g u a n ~ s i n e . ~ ~ ~ Magnesium p-diketonates form adducts with bidentate ligands such as o-phenanthroline and thus behave similarly to transition-metal derivative^.,'^ KHC03,MgC0,,4H20 has a very close approach of carbonate groups and thus a very short 0-He -0 hydrogen bond the magnesium atom being in octahedral co-ordination and the potassium " C. J . Nicholls D. S. Urch and A. N . L. Kay J.C.S. Chem. Comm. 1972 1198; F. Freund and M. Hamich Z . anorg. Chem. 1971,385 209.' O ( a ) P. S . Skell and J. E. Girard J . Amer. Chem. SOC. 1972,94,55 18; ( 6 ) K. J. Klabunde, J . Y . F. Low and M. S. Key J . Fluorine Chem. 197213 2 207; ( c ) R. D. Rieke and P. M. Hudnall J . Amer. Chem. SOC. 1972 94 7178. ( a ) K . Torkar H. Krischner and E. Hitsch Monatsh. 1972,103,744; ( 6 ) B. Eisenmann, H. Schafer and A. Weiss Z . anorg. Chem. 1972 391 241. 2 2 C. Johnson J . Toney and G. D. Stucky J . Organometallic Chem. 1972 40 C1 1 . 2 3 J . A. Nackashi and E. C. Ashby J . Organometallic Chem. 1972 35 C1. 2 4 ( a ) J.-P. Motte J.-F. Brice and J. Aubry Compt. rend. 1972,274 C 1814; J.-F. Brice, J.-P. Motte and J . Aubry ibid. p. 2166; ( b ) J . Gaude and J . Lang ibid. p. 521. 2 5 ( a ) A. Braibanti A. M. Manotti Lanfredi M. S. Pellinghelli and A.Tiripicchio Acra Crysr. 1971 B27 2261 2448 2453; (6) P. Clopath and A. V. Zelewsky Helv. Chim. Acra 1972,55,52; (c) F. Jordan and B. Y. McFarquhar J . Amer. Chem. SOC. 1972,94, 6557; (6) D. E. Fenton J . Chem. SOC. ( A ) 1971 3481 180 D. W. A . Sharp M . G. H . Wallbridge and J. H. Holloway twelve-co-ordinate with respect to oxygen ;26a distorted octahedral co-ordination is also found about magnesium in nesquehonite MgC0,,3H,0,26b and in the tris(hexafluoroacety1acetonato)magnesiumate of monoprotonated 1,8-bis(di-methy1amino)naphthalene [the proton lies in the plane of the naphthalene ring, between the two nitrogen atoms ; the corresponding copper salt is isomorphous with the magnesium deri~ative].~~‘ Alkoxymagnesium halides previously postulated in many reactions are polymeric e.g.3Mg(OR),,MgX2,nROH and are formed by interaction of the alkoxide and halide.27 3 Group I11 This year has seen the appearance of a book dealing with the development of the use of the boranes in organic chemistry and although it gives a personalised view it makes interesting reading.28 Another review in part by the same author deals with free-radical displacement reactions of organoboranes including the use of such reactions in organic syntheses and emphasizes the fact that organoboranes form a useful source of free radicals.2g Other reviews have dealt with recent studies on diborane,,’ the carbaboranes,,’ organometallic aspects of diboron and the co-ordination chemistry of thallium(~).~~ The general areas of the reactions of metal carbonyls with aluminium gallium and indium trialkyl~,,~ and the gaseous oxyhalides hydroxides and complex oxides of the Group I11 elements35 have also been reviewed.Boron.-The published work this year has again been dominated by interest in the boron hydrides the carbaboranes (including their metallo derivatives) and various heterocyclic derivatives containing boron. Variations in the binding energies of the boron 1s electrons in gaseous BF BCl, B(OMe) B,H, BMe , H,B,CO and H,B,NMe have been shown to be linearly related to the charges on the boron atoms as estimated from various calculations. The best correlation occurs with extended Huckel charges after the interatomic ‘Madelung potential’ has been included although the 1s binding energies do not show any obvious relationship to “B n.m.r.chemical shifts.36 Other calculations have shown that the hybrid orbital force field (HOFF) model can be successfully applied to adducts of borane (e.g. H,B,CO and H,B,NMe,) and substituted borane anions (BH,X, where X = F- CN- or NC-).37 Although a series of calculations of potential ’’ ( a ) G. W. Stephan C. H. MacGillavry and B. Koch Acta Cryst 1972 B28 1029; ( b ) G. W. Stephan and C. H. MacGillavry ibid. p. 1031 ; ( c ) M. R. Truter and B. L. Vickery J.C.S. Dalton 1972 395. N. Y. Turova and E. P. Turevskaya J . Organometallic Chem. 1972,42 9. H. C. Brown ‘Boranes in Organic Chemistry’ Cornell University Press London 1972. H. C . Brown and M. M. Midland Angew Chem. Internat. Edn. 1972 11 692. D. T. Haworth Endeavour 1972 31 16.A. G. Lee Co-ordination Chem. Rev. 1972 8 289. D. F. Shriver and A. Alick Co-ordination Chem. Rev. 1972 8 15. L. H. Ngai and F. E. Stafford Adv. High Temp. Chem. 1971 3 213. 27 2 8 2 9 3 0 L. H. Long Progr. Inorg. Chem. 1972 15 1 . ” 3 2 T. D. Coyle and J . J . Ritter Adv. Organometallic Chem. 1972 10 237. ” j 4 3 5 3 6 P. Finn and W. L. Jolly J. Amer. Chem. SOC. 1972 94 1540. 3 7 K. F. Purcell Inorg. Chem. 1972 11 891 The Typical Elements 181 surfaces for HeB' NeB' and ArB+ suggest that XeB' might be stable in reactions involving xenon and boron-fluorine compounds the B-F bond strength is sufficiently high to preclude any XeB' formation even when anions such as SbF6 - are used.3 The simple skeletal-electron-counting approach which allows the shapes of the polyhedral borane anions to be rationalized has now been extended to estimating bond orders and charge distribution in BgHg2-, B9Hg2- and BloHIo2-.Those skeletal atoms of lowest and highest co-ordination numbers are respectively negatively and positively charged relative to the other framework atoms.39 Another general treatment of the stereochemistries of polyhedral frameworks suggests that for both the boron hydrides and for carba-boranes the observed polyhedra adopt structures which contain boron atoms a vertices which are four- or five-co-ordinate while vertices of orders three or six are avoided as much as possible.40 A brief discussion of an attempted system-atization of borane and carbaborane chemistry using Huckel-type rules has also appeared.Boron Hydrides. This section deals with the boranes their derivatives and neutral complexes. The borane anions are discussed below. The chemical ionization mass spectra of B2H6 B4H10 B,H, B5Hll and B6H10 in methane have been studied. Two different modes of ionization are observed; for B,H6 B4H10 and BSH a dissociative proton transfer and hydride-abstraction processes occur to form (M - 1)' ions while for B,H and B6H10 proton transfer yields the (M + 1)+ ions. The results also suggest that the proton affinity of is greater than that of B,H, indicating that a relative order of Lewis acidity may be derived.42 Futher calculations on diborane suggest that many of its properties (ionization potentials shielding constants total electron densities etc.) may be estimated reliably from a minimum basis set using extended Slater orbital wave-functions.43 Other calculations have been concerned with the energies of forma-tion of diborane (- 79.8 kJ mol- l ) and the B2H,- ion (- 105.4 kJ mol-') using an ab initio SCF approach,44 and the electronic structure of the B2H5+ ion (ob-served for example in the mass spectrum of diborane) using a basis set of Gaussian orbitals allows the conclusion that the most stable structure is a planar unit with two vacant p-orbitals rather than a hydrogen-bridged unit related to dib~rane.~, So far as the chemical reactivity of borane (BH,) and diborane is concerned a mass spectrometric study of the rate of reaction of acetone with borane has shown the reaction to be bimolecular and while the product has a mass correspond-ing to BC3H,0 it is probably not an alkoxyborane but instead the adduct Me,C0,BH3.46 A similar study in a fast-flow system of the reaction between 3 8 J .F. Liebman and L. C. Allen Inorg. Chem. 1972 11 1143. 3 9 K. Wade Inorg. Nuclear Chem. Letters 1972 8 823. 40 R. B. King J . Amer. Chem. SOC. 1972,94 95. 4 ' R. W. Rudolph and W. R. Pretzer Inorg. Chem. 1972 11 1974. 42 J . J . Solomon and R. E. Porter J . Amer. Chem. SOC. 1972 94 1443. 4 3 E. A. Laws R. M. Stevens and W. N. Lipscomb J . Amer. Chem. SOC. 1972,94,4461. 4 4 J. H. Hall D. S. Marynick and W. N. Lipscomb Inorg. Chem. 1972 11 3126. 4 5 46 T. P. Fehlner Inorg. Chem. 1972 11 252. B. J . Duke and D. G. Stephens Theor. Chim. Acta 1972 26 381 182 D. W. A . Sharp M. G. H .Wallbridge and J. H. Holloway B,H and B5H9 indicates that the initial reaction is B5H9 + BH -+ B,H,,; the product either eliminates hydrogen to yield B6H10 or rearranges to the known hexaborane( 12) structure. Other results show that another initial reaction is B2H6 + BH + B3H9; this intermediate of diborane postulated to occur in the pyrolysis also eliminates hydrogen in forming B,H fragment^.^' Several reactions of diborane with nucleophiles have been further investigated. Thus while it is well known that asymmetric cleavage occurs with ammonia at room temperature when the reaction is carried out in n-hexane at 229K the borane adduct H,N,BH is formed in 22% yield and if diethyl ether is present the yield is increased to 45%.48 With water on the other hand when the dihydrate B2H6,2H20 is prepared at 143 K i.r.data obtained at low temperatures are consistent with the asymmetric cleavage product [BH,(H20),]+BH4-.49 The simple fluoroborane adducts F,HB,L (L = NMe or NEt,) have been prepared by a redistribution rea~tion,~'" and an attempt to determine the relative acceptor properties of F,BH and BH towards trimethylamine has been complicated by the fact that while BH displaces F,BH from F,HB,NMe the displaced borane disproportionates to BF and BH, although it was concluded that boron trifluoride is the strongest acceptor in the series BF F,BH FBH, and BH .50b In 1-methyl-2-substituted-piperidine-borane compounds the stereochemistry is influenced less by the substituent than for the 3- or 4-substituted derivatives and this has been related to the energetics of quaternary salt formation of substituted piperidine~.~'" Another general study of borane adducts [e.g.H,B,L (L = NMe, or PMe,)] has shown that the commonly observed upfield aromatic-solvent-induced shifts (ASIS) in 'H n.m.r. spectra of organic compounds can be reversed when the proton bears a partial negative charge since in C6D6 a downfield shift of the hydridic protons of the borane group occurs compared with the values in carbon tetrachloride ~olution.~ The question of whether the bis-borane compound with ethylenediamine H3B,NH2(CH,),NH,,BH3 exists in the gauche-or trans-conformation in the solid phase has been answered from an X-ray investigation which shows it to be the latter.52 Several new fluorophosphine-borane compounds have been identified including MeSPF,,BH ; MePF,,BH ;53a XF,P,BH3 (X = F C1 Br or I);53b and F,P(NMe,),-,,BH,.53' Relative base strengths have been established for some of the ligands as MePF > Me,NPF > MeOPF > MeSPF and in part this order of basicity has been correlated with .IBp from the n.m.r.spectra of the compounds. In the ligands F,P(NMe,),-, both the phosphorus (towards BH,) and nitrogen (towards BF,) can act as donor " S. A. Fridmann and T. P. Fehlner Inorg. Chem. 1972 11 936. '* E. Mayer Inorg. Chem. 1972 11 866. 4 9 P. Finn and W. L. Jolly Inorg. Chem. 1972 1 1 1941. ( a ) H. Mongeot J. Dazord and J . P. Tuchagues J . Inorg. Nuclear Chem. 1972,34,825; (6) J . M. Van Paasschen and R. A. Geanangel Inorg. Nuclear Chem. Letters 1972 8, 879.5 1 ( a ) R . E. Lyle E. W. Southwick and J. J. Kaminski J . Amer. Chem. Soc. 1972 94, 1413; (b) A. H. Cowley M. C. Damasco J. A. Mosbo and J. G. Verkade ibid. p. 671 5. 5 2 H. Ting W. H. Watson and H. C. Kelly Inorg. Chem. 1972 11 374. 5 3 ( a ) R. Foester and K. Cohn Inorg. Chem. 1972 11 2590; (b) R. T. Paine and R. W. Parry ibid. p. 1237; (c) S. Fleming and R. W. Parry ibid. p. 1 ; (d) R. T. Paine and R. W. Parry ibid. p. 210 (e) P. S. Bryan and R. L. Kuczkowski ibid. p. 553 The Typical Elements 183 atoms depending upon the boron compound that is used as the acceptor. The compound F4P2 ,2BH, which is stable at 228 K but unstable at 273 K has been prepared by a new route using BH,,CO as the source of b~rane.’,~ The predicted structures of Me P,BH and MeH,P,BH involving near tetrahedral arrange-ment around the boron atoms have been verified from microwave spectro-Bridge-substituted thio-diboranes p-RS-B,H have been obtained from the SCOpy.53e reaction scheme :’, KBH + (RSBH,), 353 K 7 KSR + B2H6 + K[RS(BH,),]/ \ Elimination of hydrogen occurs when excess diborane reacts with heptasulphur imide S,NH and the substituted borane S,NBH is obtained; further sub-stitution to (S,N),BH occurs in the presence of excess imide.”“ The reaction of diborane with lithium amides (LiNHR’ and LiNRi where R’ = Me Et, n-C,H, etc; R2 = Me Et n-C3H7 or i-C3H7) results in the formation of lithium borohydride and tris(amino)boranes while excess diborane yields several new p-amino-dib~ranes.~’~ In contrast n-butyl-lithium reacts with H,P,BH to yield Li(H,PBH,) which reacts further with diborane forming Li[H,P(BH,),].55‘ The related compound Li[Me,P(BH,),] reported last year reacts with the protonic hydrogen in alkylammonium chlorides eliminating hydrogen and form-ing compounds which contain a framework of (amine)-BH,-PMe,-BH .’ 5d When organic isocyanates RNCO (R = Me or Ph) are treated with diborane, cyclic trimers [H,B-N(R)(CHO)] are obtained ; a similar reaction occurs with MeNCS but PhNCS forms monomeric PhNCS,BH and dimeric (PhNCS,BH,), species.’‘ Derivatives of aluminium hydroborate namely Me,NAl(BH,) 7n or H,B(NMe),Al(BH,) ,’ 7 b result when the aluminium compounds Me,NAlH, and Al(NMe,) respectively are treated with diborane in ether solution at room temperature.’ Although borane carbonyl BH,,CO reacts similarly to carbon dioxide with primary and secondary amines it reacts differently with potassium glycinate in ethanol forming a 1 1 adduct K+[H,BC(0)NH,CH,COO]-.58 The molecular-beam mass spectra of Me,NPF ,B3H7 and F,P,B,H have been recorded and pyrolysis of the former compound affords a high-yield source of the B,H intermediate and Me,NPF ,B,H, which in turn yields B4H8 .59a 5 4 J.J . Mielcarek and P. C. Keller J.C.S. Chem. Comm. 1972 1090. 5 5 (a) M. H. Mendelsohnand W. L. Jolly Inorg. Chem. 1972,11 1944; (b) L. D. Schwartz and P. C. Keller J. Amer. Chem. SOC. 1972,94 301 5 ; (c) E. Mayer Inorg. Chem. 1971, 10 2259; (d) L. D. Schwartz and P. C. Keller ibid. 1972 11. 1931. 5 6 R. Molinelli S. R. Smith and J. Tanaka J.C.S. Dalton 1972 1363.5 7 ( a ) P. C. Keller Inorg. Chem. 1972 11,256; (b) P. C. Keller J. Amer. Chem. SOC. 1972, 5 8 5 9 ( a ) R. T. Paine G. Sodeck and F. E. Stafford Inorg. Chem. 1972 11 2593; (b) R. T. 94 4020. M. J. Zetlmeisl and L. J. Malone Inorg. Chem. 1972 11 1245. Paine and R . W. Parry ibid. p. 268 184 D. W. A . Sharp M. G. H . Wallbridge and J. H . Holloway The base replacement of dimethyl ether in Me,O,B,H by PF and CO is assisted by the presence of boron trifluoride to complex with the liberated ether.596 Further studies on n-borallyl species have included a crystal stucture determina-tion on (Me,PPh),Pt(B,H,) which shows the metal atom to be in an essentially square-planar environment with the B3H7 entity bonded asymmetrically to the metal but probably not involving M-H-B bonds6' Two interesting com-pounds Me,MB3H8 (M = A1 or Ga) have been prepared from the corresponding chloro-compounds Me,MCl by reaction with the B,H8- ion and while they appear to have static structures at room temperature at higher temperatures the protons in the B,H group show fluxional behaviour.61 A detailed investigation of the scrambling reactions of p-B,H,D and p-B,D9H has established that intramolecular hydrogen exchange occurs at two rates.The faster process involves the bridge and four of the terminal protons while the slower one involves the bridge and two remaining terminal protons attached to the 2,4-boron atoms. A possible pathway for such an exchange is illustrated in (5).62 I -3-OR ( 5 ) H B I ' (W H (6) 6 o L. J .Guggenberger A. R. Kane and E. L. Muetterties J . Amer. Chem. SOC. 1972,94, " 62 5665. J. Borlin and D. F. Gaines J . Amer. Chem. SOC. 1972 94 1367. R. Schaeffer and L. G. Sneddon Inorg. Chem. 1972 11 3098 The Typical Elements 185 Long-range coupling of the basal and apical protons in the 'H n.m.r. spectrum of pentaborane(9) has been detected using double-resonance technique^,^," and it has been suggested that the "B n.m.r. shifts in both pentaborane(9) and phenylboronic acid are determined by a resonance and inductive effect.63b The adduct of pentaborane(9) with ammonia has been characterized as B5H,,2NH ; it is stable below 273 K and is formulated as H,B(NH,),+ B4H,-,64a while a 1 1 adduct with trimethylamine 1-MeB5H,,NMe, is also unstable at room temperature and is suggested to possess a structure where the ligand is attached to a basal boron atom in a way which allows for tautomerism of the basal protons.64b The interaction of 1-SiH3B5Hg with boron trichloride yields the chlorosilyl compound 1-C1SiH2B,H without cleavage of the Si-B and the isomerization of 2,3-p-(phosphino)-BsH [phosphino = (CF,S)PCF Ph,P or MePCl] to the 1- or 2-derivative has been The tetrabutylammonium salts of the B,H,- and B6H9- ions have been prepared and their decomposition to yield the B,HI4- and B11H14- ions has been ~tudied.~" It has been shown that in addition to the well-known deprotonation of the boron hydrides the direct addition of a proton can be accomplished for hexaborane(l0) in the reaction with liquid hydrogen chloride (or bromide) the resulting cation being isolated as B6Hll+ BCl,- at low temperatures;66" both 'H and "B n.m.r.spectra of B6H10 at 126 K have resolved for the first time distinct bridging and terminal protons and boron atoms.66b A transition-metal derivative p-Fe(CO),-has been obtained as a volatile yellow crystalline compound from the reaction of Fe,(CO) with hexaborane( lo) the suggested structure being as shown in (6).67 The question as to whether any heptaboranes exist has been discussed and an examination of existing mass spectral data supports the existence of B,H .68a New 'H and "B n.m.r. data obtained at 220 MHz and 70.6 MHz respectively, for B8H12 B,H,, and B10H16 have been interpreted in terms of C, symmetry for the B skeleton in BgH12 and two B,H units bonded at the 2,2'-positions for BsHls while the spectra for BlOH16 are consistent with two B,H units boron-boron bonded at the 2,2'-po~itions.~~~ Few reactions of n-nonaborane( 15), B9H15 have been reported but recent studies show that cleavage reactions occur with acetonitrile to yield BgH12 ,NCMe and (-BNCMe-) whileammonia and sodium amalgam deprotonate the hydride forming the B,H 14- ion6,' " ( a ) T.Onak J . C . S . Chem. Comm. 1972,351 ; (b) A. R. Siedle and G. M. Bodner Inorg. Chem. 1972 11 3108. 6 4 ( a ) G. Kodama U. Engelhardt C. Lafrenz and R. W. Parry J . Amer. Chem. Soc., 1972 94 407; (b) G. Kodama ibid. p. 5807. '' ( a ) T. C. Geisler and A. D . Norman Inorg. Chkm. 1972 11,2549; ( b ) I . B. Mishra and A. B. Burg ibid. p. 664; (c) V. T. Brice H .D. Johnson D . L. Denton and S. G. Shore, ibid. p. 1135. '' ( a ) H. D . Johnson V. T. Brice G. L. Brubaker and S. G. Shore J . Amer. Chem. Soc., 1972,94 671 1 ; (b) V. T. Brice H. D. Johnson and S. G. Shore J.C.S. Chem. Comm., 1972 1128. " A. Davison D . D . Troficanto and S. S. Wreford J.C.S. Chem. Comm. 1972 1155. 6 8 (a) E. McLaughlin and R. W. Rozett Inorg. Chem. 1972 11 2567; (6) R . R. Rietz, R. Schaeffer and L. G. Sneddon ibid. p. 1242; (c) R. Schaeffer and L. G. Sneddon, ibid. p. 3102 186 D. W. A . Sharp M. G. H . Wallbridge and J. H. Holloway Further calculations on decaborane(l4) BioH14 have obtained an SCF wavefunction from a minimum basis set of Slater-type orbitals and good cor-relations of reactivity with electron distribution can be obtained in addition to an improved description of localized orbitals.69" The structural ambiguity which has existed for the B10H142- ion has been resolved since the "B n.m.r.spectrum (at 80.5 MHz) confirms the presence of two BH groups at the 6,9-positions,69b and the crystal structure of the BIoH13- ion at 103 K shows that the ion has a similar boron framework to B10H14 with a bridging hydrogen atom removed with the consequential decrease in the B-B separation to 165 pm. This is one of the shortest B-B distances reported since the same workers have re-examined the crystal structure of B6Hlo and found that the short B-B separation reported as 160 should be 163 pm.69c In the preparation of 5- and 6-halogeno-derivatives of decaborane B10H13X from the action of hydrogen halides on (R,S),BloHl steric effects become important in that the 6-isomer becomes less favoured as the size of the ligand and halogen in~rease.~' A novel compound in which dinitrogen bridges ruthenium and boron atoms has been identified as [(PPh,),Ru(N,)H,],B formed from the action of diazonium derivatives of EJlOHlo2- [namely Bl0H8(N2),] on (PPh,),Ru(N,)H .71a The crystal structure of the trichloro derivative of BloHlo2- in (NMe,)2B,oH7C13 shows that the B,, cage almost retains its D, symmetry with the three chlorine atoms attached to one apical boron and two opposite equatorial borons which are nearest to the other apical boron.71b Borane Anions and Cations.The rapid first step in the acid hydrolysis of the BH,-ion which yields H,O,BH when H,O+ comes into direct contact with BH,-, is apparently diffusion-controlled72" while the second intermediate (H20),BH2+ is stable towards hydrolysis at 195 K in the Hf concentration range of 0.1-1.1 mol 1-'.72b However the conjugate base of this latter species H20,BH20H [formed from the equilibrium (H,O),BH; H+ + H,O,BH,OH] hydrolyses to H,O,BH(OH) and this species at 237 K is further hydrolysed to B(OH) .The hydroborate ion has been isolated as the triamino-guanidinium salt [C(NHNH,),]-BH4 by treating the corresponding sulphate with sodium hydr~borate,~~" and a range of volatile cyanoboranes (BH2CN) (where x = 4 5 6 7 8 9 or 10) have been obtained from the action of hydrogen chloride on the BH,CN- ion.73b Several studies relate to the metal hydroborates and vibrational spectroscopy has been applied to the problem of determining whether the BH group is bonded 6 9 (a) E.A. Laws R. M. Stevens and W. N. Lipscomb J. Amer. Chem. SOC. 1972 94, 4467; (6) W. N. Lipscomb R. J. Wiersema and M. F. Hawthorne Inorg. Chem. 1972, 11 651; ( c ) L. G. Sneddon J. C. Huffman R. 0. Schaeffer and W. E. Streib J.C.S. Chem. Comm. 1972,474. ( a ) W. H. Knoth J . Amer. Chem. SOC. 1972,94 104; ( 6 ) F. E. Scarborough and W. N. Lipscomb Inorg. Chem. 1972 11 369. l 2 ( a ) L. A. Levine and M. M. Kreevoy J. Amer. Chem. SOC. 1972 94 3346; ( b ) F. T. Wang and W. L. Jolly Inorg. Chem. 1972 11 1933. 73 (a) L. V. Titov and M. D. Levicheva Russ. J. Inorg. Chem. 1972 17 334; (b) B. F. Spielvogel R. F. Bratton and C. G. Moreland J . Amer. Chem. SOC. 1972,94 8597. ' O B.Stibr J. Plesek and S. Hermanek Coll. Czech. Chem. Comm. 1972 37 2696 The Typical Elements 187 to the central metal atom by uni- bi- or ter-dentate hydrogen bridge while the temperature-dependence of the 'H n.m.r. spectra of M(BH,) (M = Zr or Hf) compounds has been ascribed to variations in the rate of the loB and "B quadrupole spin-lattice relaxation constants.74b Distinct bridging and terminal protons in the BH group can be observed in the 'H n.m.r. spectrum of ( Z - C ~ H ~ ) ~ -UBH, which has a triple hydrogen bridge bond at 153 K after broad-band decoupling of the ' 'B nucleus.75P The crystal structure of the U(BH,) compound has been determined from X-ray data and shows that the BH groups form a polymeric lattice in which they are linked by uranium atoms each metal atom being associated with six BH groups four of which form bridges with other metal atoms and two of which are terminal groups only.75b The reactions and equilibria involved in the mixtures of LiX salts (X = H D C1 or BH,) with aluminium hydroborate Al(BH,) have been further discussed.76 Fewer developments in the area of borane cations have appeared this year, apart from the + species mentioned above.Several new borane cations containing amides or cyanide substituents have been prepared by the following route :77 Me,M,BH,I + L + Me,M,BH,(L)+ I-(M = N or P; L = aliphatic primary amides aromatic secondary amides, or MeCN). Carbaboranes and Metallo-carbaboranes. The published papers in this area emphasize that both the carbaboranes and the interaction of carbaborane anions with metals continue to be of considerable interest.Perhaps the most significant developments lie in the areas concerned with the preparation of metallo-carbaboranes and the relationships between such compounds in that specific interconversions are now becoming possible either by polyhedral con-traction reactions brought about by base degradation or by thermal rearrange-ments. In a brief general paper the occurrence of fractional three-centre bonds in the carbaboranes is proposed to allow sensible single-valence structures to be drawn for C2B,H, 1,6-C2B,H6 and 2,4-C,B,H7 . 7 8 Two interesting methods for the preparation of carbaboranes have been reported ; one involves the pyrolysis of trimethylboron at - 773 K which yields B-methyl derivatives of the predicted nido-C4B6HlO carbaborane e.g.C,H,(BMe) ,79u the other is a low-temperature conversion of 2C into 4C carbaboranes as typified by the reaction 1,2-C2B3H7 + C,H -+ 2,3,4,5-C4B,H, which occurs at 323 K.79b 7 4 (a) T. J. Marks W. J. Kennally J. R. Kolb and L. A. Shimp Inorg. Chem. 1972 11, 2540; (6) T. J. Marks and L. A. Shimp J. Amer. Chem. SOC. 1972,94 1542. " (a) T. J. Marks and J . R. Kolb J.C.S. Chem. Comm. 1972 1019; (b) E. R. Bernstein, T. A. Keiderling S. J. Lippard and J. J. Mayerle J . Amer. Chem. SOC. 1972,94 2552. 7 6 N. Davies and M. G . H. Wallbridge J.C.S. Dalton 1972 1421. 7 7 D. L. Reznicek and N. E. Miller Inorg. Chem. 1972 11 858. '* D. S. Marynick and W. N. Lipscomb J. Amer. Chem. SOC. 1972 94 1748. 7 9 M. P. Brown A.K. Holliday and G. M. Way J.C.S. Chem. Comm. 1972 850; (b) V. R. Miller and R. N. Grimes Inorg. Chem. 1972 11 862 188 D. W. A . Sharp M . G. H. Wallbridge and J. H . Holloway The closo-carbaborane 1,5-C2B,H forms a 1 1 compound with trimethyl-amine at 195 K which decomposes at room temperature to form unidentified products,'0a and the 1 1 adduct between the same base and the closo-carbaborane 1,6-C2B4H undergoes a novel rearrangement to yield a zwitterion with the suggested structure (7).80b Negative-ion mass spectrometry is useful when it is applied to nido-carbaboranes since the ions obtained (e.g. CZB4H - or C,B,H -from nido-2,3-C2B4H8) parallel closely the chemical reactivity associated with such compounds. The negative ions are formed predominantly through a resonance-capture or a dissociative resonance-capture process.' Further data on the monoisotopic mass spectra of various carbaboranes e.g.C2B4Hs, Me2C2B,H, and Me,C2B8H, have been compiled.81' The nido-carbaborane C2B3H7 (8) reported briefly last year has been synthesized from the incomplete reaction of tetraborane(l0) and acetylene at 323 K and characterized from 'H and "B n.m.r. spectra.'2 The carbaborane (8) possesses an interesting property *' ( a ) A. B. Burg and T. J . Reilly Inorg. Chem. 1972 11 1962; ( 6 ) B. Lockman and T. Onak J . Amer. Chem. SOC. 1972 94 7923. C . L. Brown K. P. Gross and T. P. Onak ( a ) J . C . S . Chem. Comm. 1972 68; (6) J . Amer. Chem. Soc. 1972,94,8055; ( c ) E. McLaughlin and R. W. Rozett J . Phys. Chem., 1972,76 1860.D. A. Franz V. R. Miller and R. N. Grimes J . Amer. Chem. SOC. 1972,94 412. 8 The Typical Elements 189 in that it can easily rearrange to the planar anion C2B3H72- which is isoelectronic with the C,H5- ion. The rearrangement occurs on reaction of (8) with Fe(CO),, when the compound (n-C2B,H,)Fe(CO) is obtained.82 Several other metallo-derivatives of the smaller carbaboranes have been prepared; these may be classified into two types firstly those where the metal atom occupies a bridging or terminal position on the carbaborane framework and secondly those where the metal completes a closo-framework by bonding into the empty face of a nido-carbaborane. Both these types have been identified previously and now in the former class more information on the p-MR3-C2B4H7 (M = Si or Ge R = H or Me) compounds has been p ~ b l i s h e d ~ ~ " although when the bridging group is -SiH,Cl the reaction with a further mole of Na' C2B4H7- produces p,p'-SiH2-(C,B,H,), where two carbaborane fragments are linked by a silicon atom common to two three-centre B-Si bonds.83b A possible bonding scheme for the latter class using the compounds 1-MeMC2B4H6 (M = Ga or In) has been proposed following the crystal structure determination of the gallium derivative as shown in (9) and it is suggested that there is appreciable back-bonding from the metal d,,= orbital to the e2 antibonding orbital of the carbaborane ligand.84" Two further closo-compounds prepared are (n-2-MeC,B,H,)Mn(CO) ,84b from the action of Mn,(CO), on 2-MeC3B3H6 and (n-C,H,)Fe(C,B,H,) from the reaction scheme :84c NaC2B4H7 + (n-C,H,)Fe(CO),I - (n-C,H5)Fe(C0)2(C2B4H7) + NaI kv (n-C,H,)Fe(C,B,H,) 4 Oxidn' (n-C gH 5)Fe(C2B4H7) The crystal structure of the higher nido-carbaborane C,Me2B7H9 confirms almost exactly the structure proposed from n.m.r.results last year,85 in that the framework makes up a bicapped Archimedian antiprism with the 6-position missing the difference being that the two bridging hydrogen atoms are now located between the 7-10 and 9-10 positions.86" A similar framework for the C2B7 atoms occurs in the metallo-complex [Et,N]+ [Co(C,B,H,),]- where the anion is a sandwich compound with two distorted bicapped square anti-prisms one vertex (occupied by the Co atom) being common to both.86b Reports over the past two years that the 10-atom carbaborane anion C2B8HIo2- can act as a bridging ligand between two metal atoms have been 83 (a) M.C. Thompson and R. N. Grimes Znorg. Chem. 1972,11 1925; ( 6 ) A. Tabereaux and R. N. Grimes J . Amer. Chem. SOC. 1972 94 4768. 8 4 ( a ) R. N. Grimes W. J. Rademaker M. L. Denniston R. F. Bryan and P. T. Greene, J . Amer. Chem. SOC. 1972,94,1865; ( 6 ) J . W. Howard and R. N. Grimes Znorg. Chem., 1972,11,263; ( c ) L. G. Sneddon and R. N. Grimes J . Amer. Chem. SOC. 1972,94,7161. 8 5 D. W. A. Sharp M. G. H. Wallbridge and J. H. Holloway Ann. Reports ( A ) 1971,68, 253. 8 6 ( a ) J . C. Huffman and W. E. Streib J.C.S. Chem. Comm. 1972 665; ( 6 ) D. St. Clair, A. Zalkin and D. H. Templeton Inorg. Chem. 1972 11 377 190 D. W. A . Sharp M. G. H . Wallbridge and J H.Holloway substantiated from the novel reaction : (n-CSH,)Co(C,B8H10) + CoC1 + Na+(CsH5)- + (n-CSHS)Co(C2B8H1 o)Co(n-C5H5) The product which probably contains a 12-atom polyhedral fragment CoZCZB8, shows that polyhedral expansion reactions often used to prepare metallo-carbaboranes from closo-carbaboranes can also be applied to the closo-metallo-carbaboranes themselves.87a The geometry of the ligand (C2B,HloC5HsN)- in the sandwich compound [Et,N]+[(CzBgHl I)Co(C,B,HloC5HsN)]- has been determined from an X-ray study and is shown in Apart from the polyhedral expansion reaction described above two further methods for preparing metallocarbaboranes have appeared. One involves the intermediate icosahedral anion [TIR' RZC2B,Hg] - which yields closo-metallo-carbaboranes on treatment with halogeno-derivatives of the transition metals.The other involves the direct insertion of a nucleophilic metal species into suitable closo-carbaboranes thus closo-1,8-Me,C2B9H9 on treatment with Pt(PEt3) yields (PEt,),Pt[Me,C2BgH9] where the Pt" ion is suggested to occupy the vacant icosahedral site above a do-1,7-Me2C2BgHg fragment.88 In contrast P"" ( a ) W. J . Evans and M. F. Hawthorne J.C.S. Chem. Comm. 1972 611; ( 6 ) M. R. Churchill and K. Gold ibid. p. 901. J. L. Spencer M. Green and F. G. A. Stone J.C.S. Chem. Comm. 1972 1178 The Typical Elements 191 to these expansion reactions the opposite approach of using polyhedral con-traction reactions is also proving successful. While these types of reactions are known for the carbaboranes themselves they have also now been extended to the metallocarbaborane compounds and the first example of a polyhedral contraction where a polyhedral metallocarbaborane is transformed into its next lower homoiogue by the formal removal of a BH2+ group followed by a two-electron oxidation has been identified in the base degradation of [LCo{ x-(3)-1,2-C2BgHl,}]' to [LCO(~-(~)-~,~-C,B~H~~)]~ where L = CsH5- z = 0; or L = (3)-1,2-C2BgHIl2- and z = - l.89a*b In the area of dicarbollyl complexes the thermal rearrangement of (x-C5H5)-Co[n-(3)-1,2-C2BgH 1] and related compounds at 673-973 K yields compounds which contain all nine isomeric dicarbollyl ligands which are formed by migration of the cage C atoms over the polyhedral surface.90a Thermal decomposition of the arenediazonium salts [ArN,] [7t-7 8-C2BgH ,),Co] (Ar = Ph or C,H,Me) at 373 K affords new compounds of the type [Me4N] [(n-7 8-C2BgHlo)2C6H4C~] where the aryl group C6H4 is believed to occupy a bridging position between two C2B9Hlo fragments.90b In the heteroatom carbaborane ligands (l,7-B9H9CHE)2- (E = P or As) the phosphorus or arsenic atom can act as a donor site since when the [( 1,7-B,H,CHE),FeI2- anion is irradiated in the presence of a Group VI metal carbonyl the complex [( 1,7-B,H9CHE)M(C0)5]2-Fe2- is formed with the M(CO) fragment o-bonded to the carbaborane ligand."' A further discussion has appearedgod*' of the bonding and structure of the two aluminium compounds C,B,H ,AlMe2 and C2B9H ,AlEt reported last year.Polyhedral contraction reactions using base degradation reactions also occur with (7c-C,H,)Co(C2BloHl,) to yield [(n-C,H,)Co(CB,H,)]- this being a unique example of the removal of one C and three B atoms from a metallo-carbaborane and the CB,H,3- ligand may be classified into the general class CB,H,+13- of which the only other known example is CBloHl13-.91a The starting material first prepared last year is known to exist in three isomeric forms and the crystal structure of the red isomer shows the presence of a 13-vertex docosahedron in which the Co"' ion is linked directly to a C2B4 hexagon (1 1).The steric strain caused by such an arrangement becomes apparent in several distortions and irregularities in the remaining distances and angles of the cage framework.91b The bis-lithio salt of o-carbaborane LiCB oH,oCLi reacts with 1,3-dibromopropane to yield ( ~ L - C H ~ ) ~ - C ~ B ~ ~ H ~ ~ and this in turn forms metallocarbaboranes much like the dicarbollyl anion of the general types [M"+(C5B9H15)2]R-4 or (n-C5H5)M11'(C5BgH15).92a An unusual migration of the C,B,,H12 fragment occurs when thecompound (C2Bl0Hl2)Fe(n-C,H,)(CO), 8 9 C.J . Jones J . N. Francis and M. F. Hawthorne ( a ) J . C . S . Chem. Comm. 1972 900; ( 6 ) J . Amer. Chem. Soc. 1972 94 8391. 90 (a) M. K. Kaloustian R. J . Wiersema and M. F. Hawthorne J . Amer. Chem. Sac., 1972 94 6679; ( 6 ) J . N. Francis C. J. Jones and M. F. Hawthorne ibid. p. 4878; ( c ) D. C. Beer and L. J . Todd J . Organometallic Chem. 1972,36,77; (d) M. R. Churchill and A. H . Reis J.C.S. Dalton 1972 13 14; ( e ) ibid.p. 13 17. 9 1 ( a ) D. F. Dustin and M. F. Hawthorne J.C.S. Chem. Comm. 1972 1329; (6) M . R. Churchill and B. G. DeBoer ibid. p. 1326 192 D. W. A . Sharp M. G. H. Wallbridge and J. H . Holloway - w -(11) (12) is treated with halogen at 293 K and the new compound (12) is ~btained.’~’ Several a-bonded platinum complexes L,Pt( 1-Me-1,2-C2B ,H (where L = PPh, PPh2Me PMe, etc.) have been obtained via the action of the lithiocarbaborane on the L,PtC12 derivative^.'^' The crystal structure of the bis-carbaborane complex [NEt,]+[Co(C2Bl,Hl,),],- shows the metal atom to be surrounded by four C2B1 icosahedra in a tetrahedron but it is interesting that while the four nearest neighbours to the cobalt are carbon atoms these form a distorted tetrahedron e.g.one C-Co-C angle is 150.4” and since one boron atom is also quite close to the central atom the possibility of having 4 carbon atoms and one Co-H-B bond in the metal co-ordination sphere A simplified preparation of the o-carbaboranes C,B,,H, has been de~ised,’~’ and various bromo-substituted o-carbaboranes react with pyridine the un-substituted carbaborane being unreactive forming the 3,6-dipyridine derivatives, which are isoelectronic with the C2B10H122- anion.93b The reduction of o-carbaborane with a Na-THF mixture yields C2B,,H ,’- which on hydrolysis forms two isomeric C2Bl,H,,- ions one of which is unstable and rapidly inter-9 2 9 3 ( a ) T. E. Paxson M. K. Kaloustian G. M. Tom R. J . Wiersema and M. F. Hawthorne. J . Amer. Chem. SOC. 1972,94,4882; (b) L.1. Zakharkin L. V . Orlova B. V. Lokshin, and L. A. Fedorov J . Organometallic Chem. 1972 40 1 5 ; (c) R. Rogowski and K. Cohn lnorg. Chem. 1972,11 1429; (d) R. A. Love and R. Bau J . Amer. Chern. Soc., 1972.94 8274. (a) H. Beall lnorg. Chem. 1972 11 637; (6) J . Plesek T. Hanslik F. Hanousek and S. Hermanek Coll. Czech. Chem. Comm. 1972,37,3403; ( c ) G . B. Dunks R. J. Wiersema, and M. F. Hawthorne J.C.S. Chem. Comm. 1972 899 The Typical Elements 193 converts to the other stable form at 300 K. These ions may contain a methylene-type carbon atom within the polyhedral framework.93c Boron-Carbon Compounds. The structure of the cobalt-borabenzene complex Co( H,CSBOMe) determined from X-ray studies confirms that the C,B rings sandwich the metal atom and that the rings deviate only slightly from a planar The preparation of the 9-phenyl-9-bora-anthracene anion (1 3) has been achieved by allowing the neutral compound to react with LiBu‘ in THF.The ion is obtained as the lithio salt co-ordinated by 3.5 moles of THF and this solvent cannot be removed under The related lO-phenyl-9,lO-dihydro-9-bora-anthracene has also been prepared from tris-(2-benzhydryl-pheny1)boro~in.~~‘ The cyclic boratropylium and boracyclopentadienyl cations have both been identified in the mass spectra of cyclic derivatives of organo-boranes containing at least one B-N bond e.g. PhB-R’-CH,-C(HR2)-NR3 or Ph~-R’-(CH,),-~H (R’ = 0 S or NH).94d I Ph Mixed organoboranes R$BR2 can be easily prepared in high yield from the accessible thioboranes RiBSR by treating the latter with LiAlH in the presence of a suitable ~ l e f i n .~ ’ ~ Although as last year hydroboration will not be covered in this review it is worthwhile highlighting two papers. One deals with the measurement of the relative rates of the first and second steps of hydroboration, and it is observed that in the sequence BH + olefin -+ RBH -+ R,BH the rate of the second reaction is greater than that of the first and it is also concluded that for hydroboration reactions carried out in THF solution the initial reaction involves the adduct BH,,THF and the alkene.95b The other paper reports the isolation of the first monomeric dialkylborane dithexylborane (Me,C,H),BH, prepared from tetramethylethylene by the reaction scheme 9 5 c 9 4 ( a ) G. Huttner and B.Kreig Angew Chem. Internat. Edn. 1972,11,42; ( b ) P. Jutzi ibid., p. 5 3 ; ( c ) R. Van Ween and F. Buckelhaupt J . Organometallic Chem. 1972 43 241 ; (d) R. H. Cragg J . F. J. Todd R. B. Turner and A. F. Weston J.C.S. Chem. Comm., 1972 206. 9 5 ( a ) A. Pelter and D. N . Sharrocks J.C.S. Chem. Comm. 1972 566; ( 6 ) D. J. Pasto B. Lepeska and V. Balasubramaniyan J . Amer. Chem. SOC. 1972 94 6090; ( c ) E. Negishi J. Katz and H. C. Brown ibid. p. 4025 194 D. W. A . Sharp M. G. H. Wallbridge and J. H. Holloway H H \ / \ H H Other studies relate to the many diverse properties of the organoboranes. A series of para-substituted phenyl-dimesitylboranes have been prepared by the action of phenyl-lithium on the (Me,C,H,),BF derivative in order to study the variation in the photochemical behaviour with the substit~ent,’~~ and other workers have found that the U.V.spectra of para-substituted tribenzylboranes (XC,H,CH2),B contain an absorption in the region 240-285nm which is assigned to intramolecular charge transfer from the aryl group to the empty boron 2p-0rbital.~~’ An e.s.r. study of the trimesitylborane anion indicates some non-planarity in the rings probably due to steric hindrance between the ortho-methyl groups.96c A novel approach has shown that it is possible to stabilize boron-containing carbanions obtained from the action of a base having large steric requirements on an organoborane according to the scheme :97 The electrolysis of alkyl borates in the presence of olefins is of interest for alkyla-tion reactions and the anodic oxidation of trihexylborane in the presence of methoxide ions using a graphite electrode at 268 K yields hexyl radicals which dimerize to produce dodecane C 2H26 but at 253 K in the presence of butadiene only a small amount of dodecane is obtained the main products arising from the addition of C6H; to the butadiene radical cation to form C6R13-C4Hk followed by C7HI5CH=CHC7Hl5 etcg8 The first addition of a triorganoborane to a carbonyl group has been achieved using monomeric formaldehyde at 273 K Bu;B + CH20 + Bu”,OCH + CH,CH2CH=CH2 (1) Bu BOCH 2 B ~ n (2) o b y 6 (a) J.C. Doty B. Babb P. J. Grisdale M. Glogowski and J. L. R. Williams J . Organo-metallic Chem. 1972 38 229; ( 6 ) B. G. Rarnsey N. K. Griffith and H. van Willigan, J . Chem.Phys. 1972 57 86. 97 M. W. Rathe and R. Kow J . Amer. Chem. SOC. 1972,94,6854. 98 H. Shafer and D. Kock Angew Chem. Infernat. Edn. 1972 11 48 The Typical Elements 195 [reaction (211 although the presence of oxygen is required probably to generate alkyl free radicals otherwise reaction (1) occurs.99a The rate constants for the primary initiation state of borane autoxidation have been shown to increase through the series BuiB < BuiB < (CsH11)3B; the reactions are first-order in both borane and oxygen.'" The anions of the general type (BR,CN)- have been shown to co-ordinate to Cu' and Ag' salts forming compounds such as (Ph3P),M(NCBR3) which contain an M-N bond in both the solid and solution phases. The related compound (Ph,P),Cu(NCBH,) on the other hand appears to form a dimeric molecule, and preliminary X-ray results suggest the structure shown in (14).'0° f j H H n x /y B Ph (14) L = Ph,P (15) Two convenient routes to alkylboron halides have been reported.Trialkyl-boranes which have been prepared by the hydroboration of terminal cyclic or bicyclic olefins using a slight excess of borane react rapidly with boron trichloride at 383 K yielding RBCl compounds ''la and a-bromoethyldiethylborane under-goes very rapid rearrangement to s-butylethylboron bromide at 298 K under the influence of aluminium bromide.' O1 Finally the intriguing rearrangements of hydrocarbon ions which have been detected in the mass spectra of several boron compounds have now been found also for the phenylborolans (15) where X = Y = 0; X = 0 Y = S; or X = Y = S and again the tropylium ion C7H7 + has been detected.lo2 Compounds containing B- N and B -P Bonds. Ap ab initio MO study of t4e ygt unisolated iminoborane HBNH predicts a linear structure with a polar B=N bond which is best represented as a triple bond and which is comparable in v 9 ( a ) N. Miyaura M. Itoh A. Suzuki H. C. Brown M. M. Midland and P. Jacob J . Amer. Chem. SOC. 1972,94 6549; (6) P. B. Brindley and J . C. Hodgson. J.C.S. Chem. Comm. 1972 202. l o o S. J. Lippard and P. S. Welcker Inorg. Chem. 1972. 11 6 . ' " I ( a ) H . C . Brown and A. B. Levy J . Organometalfic Chem. 1972 44 233; (6) H. C. Brown and Y. Yamamoto J.C.S. Chem. Comm. 1972,71. R. H. Cragg G . Lawson and J . F. J . Todd J.C.S. Dalton 1972 878 196 D.W. A . Sharp M. G. H. Wallbridge and J. H. Holloway strength to the C-C linkage in a~ety1ene.l'~~ The low barrier to thermal isomer-ization in aminoboranes often prevents the isolation of cis- and trans-isomers, but now the trans-isomer of (PhCH,)(CH,)B+=N(Ph)(CH,Ph) at 251 K has been partially converted (15% in 10min) into the cis-isomer by irradiating at 253.7 nm.'03' A study of the I4N n.m.r. spectra of a series of simple aminoboranes, e.g. B(NR,), R'B(NR;), and R,BNH, has shown that a decrease in the shielding of the 14N nucleus occurs with increasing B-N bond order and that the signals are generally broad e.g. h for Et,BNMe is 222 H Z . " ~ ~ The n.m.r. spectra of some pyrazolyl compounds e.g. RB(pz),Mo(CO),(n-C,H,) (where pz = 1 -pyrazolyl) have indicated stereochemical non-rigidity in the pyrazolyl ligand,103d-f and the crystal structure of one complex [H2B(3,5-dimethyl-pyrazolyl)]Mo(CO),(C,H,) shows a trihapto-C,H ring and a severely bent boat form of the pyrazolyl chelate ring with a three-centre two-electron B-H-Mo bond.103g The synthesis of a range of pyrazolyl ligand compounds e.g.(pz)B(pz),Mn(CO),-,L pz = 1-pyrazolyl; L = P(OMe), n = 1 or 2; L = PMe or PBu'; n = 11 has been described using a photochemical reaction between (pz)B(pz),Mn(CO) and the ligand L.'03" Various reactions of aminoboranes reported include their use in the synthesis of sulphenamides according to the scheme :' 04a (R,N),B + 3PhSOMe -+ 3R,NSPh + B(OMe), A similar reaction with tertiary alkyl alcohols yields tris(t-a1kyl)boranes.I 04' Insertion reactions occur when CO, or COS is allowed to react with B(NR,), compounds and compounds such as Me,NB[OC(S)NMe,] and B[OC(O)-NHNMe,] are ~ b t a i n e d ." ~ ~ The halogen derivatives (R;N),BX - yield monomeric compounds (RiN),B(MRi) - (where M = P As or Sb R' = Me, R2 = Me or Et) on reaction with the lithio reagents LiMR~.'"" Cleavage of the B-N bond in the dimeric aminoborane (Me,NBH,) occurs on treatment with trimethylaluminium and in addition to the formation of (Me,NAlMe,) , (Me2A1H) and BMe the compound Al,Me,(NMe,),H is observed which consists of an eight-membered ring composed of Al,N,H atoms.105' Further properties of the monomeric methyleneaminoboranes e.g. BuiC NBPh have also been p~blished.'~~' New compounds containing €3-N bonds have been prepared by the action of PhBC1 or BCl on SPF,NH or P,N,F,NH, when boranes such as (SPF,NH),B and (P,N,F,NH),BPh are obtained.'05d l o 3 ( a ) N.C. Baird and R. K. Datta Inorg. Chem. 1972 11 17; (6) K. G . Hancock and D. A. Dickinson J . Amer. Chem. SOC. 1972,94,4396; ( c ) W. Beck W. Becker H. Noth, and B. Wrackmeyer Chem. Ber. 1972 105 2883; (d) P. Meakin S. Trofimenko and J . P. Jesson J . Amer. Chem. Soc. 1972,94 5677; ( e ) J . L. Calderon F. A. Cotton and A. Shaver J . Organometallic Chem. 1972 37 127; (f) ibid. 1972 38 105; (g) F. A. Cotton J . L. Calderon M. Jeremic and A. Shaver J.C.S. Chem. Comm. 1972 727; (h) A. R. Schoenberg and W. P. Anderson Inorg. Chem. 1972 11 85. l o 4 ( a ) R. H. Cragg J. P. N. Husband G. C. H. Jones and A. F. Weston J . Organo-metallic Chem.1972 44 C37; (6) I. Kronawitter and H. Noth Chem. Ber. 1972 105, 2423; (c) A. Meller and A. Ossko Monatsh 1972 103 577. ( a ) W. Becker and H. Noth Chem. Bet-. 1972,105 1962; ( b ) J . D. Glore R . E. Hall and E. P. Schram Inorg. Chem. 1972 11 550; (c) M. R. Collier M. F. Lappert R. Snaith, and K. Wade J.C.S. Dalton 1972 30; ( 6 ) H. W. Roesky Chem. Ber. 1972,105 1726. l o The Typical Elements 197 The crystal stucture of dimeric (Ph,PBI,) shows a four-membered non-planar B-P ring with a dihedral angle of 30" the complete molecule possessing an axis of near two-fold symmetry.'06 Compounds containing B-0 and B-S Bonds. The variation in the electrical conductivity of an H,O-B,O melt over a range of compositions has led to the suggestion that two conduction mechanisms exist; in a B(OH) solution a proton-jump process occurs while in a melt of B,O containing only a trace of water the usual ionic migration is present.'07" A study of boric acid-borate equilibria using a hydrogen-electrode concentration cell suggests that in dilute solution the equilibrium B(OH) + OH- S B(OH),- occurs while in more concentrated solution B2(OH),- B,(OH),O- and minor amounts of B,(OH),,,- and B,(0H),,3- occur.1o7b The B-0 bond dissociation energy in B(OPh) has been calculated as 437 kJ mol- from thermochemical data which makes it a relatively weak bond compared with other B(OR) C O ~ ~ O U ~ ~ S .' ~ ~ ~ The crystal structure of tetra-acetyl diborate (AcO),B.O.B(OAc) shows it to consist of two distorted boron-oxygen tetrahedra sharing a vertex with all other vertices connected to the carbon atoms of the four acetoxy-groups; two of these groups have only one B-0-C bond whereas the other two have two such bonds."*" The difference between B203 and B,S arises in part from the lack of interaction of the B atom with the fourth S atom in the solid phase of B2S3 this suggestion having been made following v.p.measurements of B,S,(g) and B4S,(g) over B,S as determined mass spectrometrically.'08b Another difference of B(SMe) from B(OMe) has also been detected by this technique in that while the latter fragments into relatively few ions due to the strong B-0 bond the former gives many more ions together with high yields of rearrangement ions such as MeSCH,' and MeSSMe+' (ref. 109~). The novel use of thioboranes in the preparation of borazines by interaction with hydroxy- or mercapto-amines has been reported.'0gb A "B n.m.r.study of potassium tetraborate K20,5B,0 ,8H,O at concentra-tions > 0.4 moll- ' shows the presence of an equilibrium between B(OH) and B(OH)4- possibly involving B303(OH)4- or B,O,(OH),-.' The crystal structure of potassium diborate K,0,2B203 shows a single three-dimensional borate anion framework composed of mutually linked BO triangles making up diborate and triborate groups in which 2 of the 3 boron atoms are tetraco-ordinated.' Ob I o 6 G. J . Bullen and P. R. Mallinson J.C.S. Dalton 1972 1143. l o ' ( a ) H. Kodama T. Yokokawa and K . Niwa Bull. Chem. SOC. Japan 1972 45 776; (6) R. E. Mesmer C. F. Baes and F. H . Sweeton Znorg.Chem. 1972,11,537; ( c ) J. T. F. Fenwick and J. W. Wilson J.C.S. Dalton 1972 1324. ( a ) A. D. Negro L. Ungaretti and A. Perotti J.C.S. Dalton 1972 1639; (6) H. Chen and P. W. Gilles J. Phys. Chem. 1972 76 2035. l o 9 (a) R. H. Cragg J. F. J. Todd and A. F. Weston J.C.S. Dalton 1972 1373; (b) R. H. Cragg and A. F. Weston J.C.S. Chem. Comm. 1972 79. ' l o (a) H. D. Smith and R. J . Wiersema Znorg. Chem. 1972 11 1152; (6) J . Krogh-Moe, Acra Crysr. 1972 B28 3089 198 D. W. A . Sharp M. G. H. Wallbridge and J. H. Holloway Compounds containing Boron-Halogen Bonds. This section discusses the boron trihalides their co-ordination compounds the sub-halides and the tetrahalogeno-borate ions. The nature of metal surfaces has been studied by the adsorption of BF and BCl ; the former is adsorbed without dissociation on V Fe Ni Cu and Pd films ; the complex formed is stable in air but carbon monoxide will displace the BF, from Ni and Pd but not V or Cu surfaces.' Calculations using the Long-Plane equation which relates M=X bond polarizability to covalent character satis-factorily for Group IV compounds have shown that the equation also provides reasonable agreement for the boron trihalides (except the fluoride). ' ' The use of the boron halides as synthetic reagents for halogen-transfer reactions has been further exploited for the preparation of rhenium halides,' [L2PtXIz2+ (X = F C1 or Br; L = Bu:P) cations,''3b and F,P(OR),_. from ReCl, L,PtY (Y = C1 Br NCO or N,) and P(OR) respectively. Some interesting reactions occur with transition-metal compounds ; with Co,(CO) the adducts BX ,NEt (X = C1 or Br) form cluster compounds of the type Co3(CO),-[COBCl,NEt,] (16) and CO,(CO)~[COBC~,NE~,] depending on the molar (16) L = BC12N(C2H5)3 ' I 1 R.Sheets and G. Blyholder J . Amer. Chem. SOC. 1972 94 1434. 'I2 R. J. H. Clark and P. D. Mitchell Inorg. Chem. 1972 11 1439. ' I 3 ( a ) M. A. Bush P. M. Druce and M. F. Lappert J.C.S. Dalton 1972 5 0 0 ; ( b ) P. M. Druce M. F. Lappert and P. N. K. Riley ibid. p. 438; (c) H. Binder and R. Fischer, Z. Naturforsch. 1972 27b 753 The Typical Elements 199 ratios of the reactants used.' lbVb With the zerovalent platinum complex Pt(PPh,) boron trichloride forms a 1 2 adduct (PPh,),Pt(BCl,) and the 1 1 compound (PPh3)2PtBC13 was also obtained by displacement from (PPh3),-PtSiF .' 14' Halogen exchange occurs as above when the carbonyls M(CO),-PPh,SnMe (M = Cr Mo or W) react with the trihalides and the corresponding M(CO),PPh,SnMe,Cl or M(CO),PPh,SnMeBr complexes are obtained with BCl and BBr respectively.' 14d The silylamine (Me,Si),NH reacts with BF below 273 K forming the simple 1 1 adduct but above 273 K elimination of Me,SiF occurs and Me,SiNH ,BF, together with borazines e.g.F,B,N,(SiMe,) are formed.' 15a The same 1 1 adduct in the presence of PriEtN,BF eliminates HF to form (Me,Si),NBF,, and this in turn reacts with Me,SiNR (R = Me Et Pr" or Bun) at 423 K yielding (Me,Si),NB(F)NR,. ' ' 5b The reactivity of the trihalides towards silanes appears to increase through the series BF < BCl - BBr since BCl is reduced by the MeSiH while BF is not and BBr is reduced also by ClSiH .' 15' The gaseous species produced by heating silicon tetrafluoride with silicon (or silicon carbide) at 1473-2123 K when condensed with BF at 81 K produces F,SiBF in addition to the known mixed fluoride F3SiSi(F2)BF,.'*5d The crystal structure of the benzoylacetonate BF compound (17) obtained from interaction of the ligand with BF, shows the boron atom to be in a near tetrahedral environment and chelated by the two oxygen atoms.''6 With regard to the co-ordination compounds formed by the boron trihalides, the mechanism of formation of the Me,N,BX and mixed halide compounds Me,N,BX,Y,- has been studied and the results suggest that halide exchange occurs without B-N bond dissociation (contrary to earlier suggestions) at least in solution and only if an excess of the boron halide is present.In the gas phase it is likely that the B-N bond does dissociate since here exchange of the B atom does occur." 7 a The slower exchange rate using bases containing N ligand atoms, compared with 0 donor systems allows all twenty possible adducts of trimethyl-amine with mixed boron halides to be identified using 'H n.m.r. spectra."7b This slow rate of exchange has also allowed the determination of the stoicheio-metry and relative basicity of a number of nitrogen ligands towards BF and BCl, using 'H and "F n.m.r. In mixtures of X,B,OMe (X = F or Cl), near statistical amounts of the mixed halide adducts are obtained in mixtures of the trifluoride and trichloride adducts as identified from "B or "F n.m.r.spectra, ' l 4 ( a ) G. Schmid and B. Stutte J . Organometallic Chem. 1972,37,375; (b) G . Schmid and V. Batzel ibid. 1972 46 149; ( c ) T. R. Durkin and E. P. Schram Inorg. Chem. 1972, 11 1054; (d) H. Noth and S. N . Sze J . Organometallic Chem. 1972,43 249. " ' G. Elter 0. Glemser and W. Herzog ( a ) Chem. Ber. 1972,105 115; ( 6 ) Inorg. Nuclear Chem. Letters 1972,8 191 ; ( c ) M. A. Ring ibid. p. 421 ; (6) D. L. Smith R. Kirk and P. L. Timms J.C.S. Chem. Comm. 1972 295. ( a ) B. Benton-Jones and J. M. Miller Inorg. Nuclear Chem. Letters 1972 8 485; ( b ) B. Benton-Jones M. E. A. Davidson J. S. Hartman J . Klassen and J. M. Miller J.C.S. Dalton 1972 2603; (c) A. Fratiello R. E. Schuster and M. Geisel Inorg.Chem. 1972, 11 1 1 ; (d) M. J. Bula D . E. Hamilton and J. S. Hartman J.C.S. Dalron 1972 1405; ( e ) J. E. Drake and B. Rapp ibid. 1972 2341. ' l d A. W. Hanson and E. W. Macaulay Acta Cryst. 1972 B28 1961 200 D . W. A . Sharp M. G. H. Wallbridge and J. H. Holloway but decomposition reactions occur when B-Br or B-I bonds are Further studies of exchange processes have been made on PH,-BC1,-BBr and other mixtures of the trihalides and complexes such as H,P,BClBrI and H,P,BX,Y (X # Y = C1 Br or I) have been identified.'17e The 'H n.m.r. spectra of mixtures of BF,-MeOH in liquid sulphur dioxide show that at molar ratios MeOH BF > 2 1 the products are the 1 1 adduct MeOH,BF and MeOBF,- MeOH,+.1'8" Other 1 1 adducts have been characterized with tetramethylurea (where 0 acts as the donor site),' ' 8b aromatic aldehydes,' ' *' and phosphites (RO)3P.118d The kinetics of the exchange reaction RY + BX,+ RX + BX,Y (R = Pr" Pr' Bun Bus or Me,Si ; Y = C1 or Br ; X = Br or I) where X is heavier than Y have been studied in carbon tetrachloride or cyclohexane solution using 'H and "B n.m.r.spectra and the results suggest that the inter-mediate RY,BX is i n v ~ l v e d . ' ~ ~ The direct reaction of Fe" salts dimethyl-glyoxime and BF ,Et,O [or B(OH),] in an alcohol leads to encapsulated metal complexes according to the scheme : Fez+ + 3dmgH + 2B(OH) + 2ROH -+ [Fe(dmg),(BOR),] + 2H+ + 6HOH (R = Me Et Pr' Bun or OH) With BF ,Et,O the compound [Fe(dmg),(BF),] is obtained and the cage-like nature of this compound has been established from unpublished X-ray data.'" Alkyl- and aryl-seleno-halogenoboranes e.g.MeSeBI and (PhSe),B have been prepared by the action of the organoselenane on the alkyl boron halides; their properties differ in that MeSeBI and MeSeB(Me)I are stable trimers (MeSe),BI and MeSeB(Ph)I are monomeric and the aryl compounds ArSeBI exhibit low thermal stability and decompose to (ArB),Se, or (ArSe),B in the case of the chloro derivative ArSeBCI .12 l a y b As in the case of the trihalides exchange reactions have also been observed in the tetrahalogenoborate ions BX,-(X = F C1 Br or I) using "B n.m.r. spectro-scopy and signals arising from the mixed ions have been observed.' A mixture of BC1,-PC1,-NH,Cl yields chlorophosphazonium tetrachloroborates [Cl(C1,P=N),PCl3]BCl ,' 2 2 b and dioxygenyl tetrafluoroborate established as O,+BF,- from i.r.studies reacts with xenon near 173 K to form a white solid which decomposes at 243 K to form another solid believed to be FXeBF which is assumed to contain a covalent Xe-B bond.'''' The crystal structure of ''* ( a ) K. L. Servis and L. Jao J . Phys. Chem. 1972,76 329; ( b ) J. S. Hartman and G. J. Schrobilgen Canad. J . Chem. 1972 50 713; (c) M. Rabinovitz and A. Grinvald J . Amer. Chem. SOC. 1972 94 2724; (d) T. Reetz Inorg. Chem. 1972 1 1 650. M. Goldstein L. I. B. Haines and J. A. G. Hemmings J.C.S. Dalron 1972 2260. S . C. Jackels D. S. Dierdorf N. J. Rose and J. Zekter J.C.S. Chem. Comm. 1972 1291. W. Siebert and A. Ospici ( a ) Chem. Ber. 1972 105 454; ( 6 ) ibid. p. 464. (a) J.S. Hartman and G. J. Schrobilgen Inorg. Chem. 1972 11,940; ( 6 ) K. Niedenzu, I . A. Boenig and E. B. Bradley Z . anorg. Chem. 1972,393,88; ( c ) C . T. Goetschel and K. R. Loos J. Amer. Chem. SOC. 1972,94. 3018. ' The Typical Elements 201 [Ni(en),(H,O)BF,]BF reveals a cis-configuration for the two ethylenediamine molecules about the nickel atom with the remaining octahedral positions being occupied by H,O and BF, the latter being bonded through a fluorine bridge atom as Ni-F-BF .12, The action of copper vapour on boron trichloride yields diboron tetrachloride, B2C14 when the two reactants are condensed onto a surface at 81 K,124a and the action of this reagent on various cyclopropanes leads to ring cleavage and products which probably contain the dichloroboryl groups in the 1,3-positions on the hydrocarbon chain e.g.Cl,B.(CH,),.BCl .12,' Another study of the action of B,Cl on SiC1 or SiF at 81 K shows that novel boron-silicon com-pounds such as Cl,SiBCl are formed while when CO or PF are also present, other compounds (SiCl,),(BCl,)B,L (L = CO or PF,) are formed although in very low yield. 24c The condensed compound B,F which had been previously characterized has also been further studied and it is now believed to possess the structure shown in (18) which would be consistent with its reactions with a series of ligands when adducts of the type (BF,),B,L (L = CO PF PCI PH ASH,, or SMe,) are formed.' 24d Heterocyclic Compounds containing Boron. This year the heterocycles containing boron-carbon bonds as found in the bora-anthracene ion for example are discussed in the section dealing with boron-carbon compounds.The compounds are again discussed in the order of B-N B-0 and B-S heterocycles. The electronic structure of the ground state of the parent tetrazaboroline H,N,BH has been calculated,'25u and a summary of several routes to the B-halogen (or -pseudohalogen) derivatives has been given.'25b In the borazine compounds another calculation of the electronic energy shows that the planar D, molecule is preferred energetically and supports the generally accepted view A. A. G. Tomlinson M. Bonamico G. Dessy V. Fares and L. Scaramuzza J . C . S . Dalton 1972 1671. 1 2 4 ( a ) P. L. Timms J . C . S . Dalton 1972 830; (b) M. Zeldin and A. Rosen J . Organo-metallic Chem. 1972,34,259; (c) R.W. Kirk D . L. Smith W. Airey and P. L. Timms, J . C . S . Dalton 1972 1392. ( a ) D. R. Armstrong P. G. Perkins J . M. Scott and J. J . P. Stewart Theor. Chim. Acta, 1972 26 237; ( b ) B. Hessett J. B. Leach J. H. Morris and P. G. Perkins J . C . S . Dafron, 1972 131 202 D. W. A . Sharp M . G. H . Wallbridge and J. H . Holloway that the B and N atoms carry positive and negative charges respectively.'26a From the 'H n.m.r. spectrum over a range of temperatures the broad lines have been analysed to yield estimates of the nuclear quadrupole coupling constants' 26b and spin-lattice relaxation times.' 26c The chemical ionization mass spectrum of borazine has yielded a value of the proton affinity as 853 kJ mol-' so that it should be considered as a relatively strong base.'26d Evidence for a borazyne intermediate B,N,H in the photochemical decomposition of borazine has been suggested to occur via the scheme : B3N3H6* + B3N3H6** -+ B3N3H4 + H2 The B,N,H6** species is suggested to arise from an internal conversion process and is a molecule in a vibrationally 'hot' ground state.12' Several new borazines have been prepared including the ortho- and para-substituted isomers H,ClB,-N3H2Me and the relative amount of each isomer (30% ortho- and 70% para-) suggests that some directive influence is operating in the original preparation from H,B,N,H,Me and HgC1 .128a Routes to 1,3,5-triaryl- and 1,3,5-triaryl-2,4,6-trichloro-borazine have been devised and it has been found that borazine formation is inhibited by 2-ortho-substitution when compounds such as (ArNH),BH and ArNHBCl are obtained instead.'28b The NN'N"-trimethyl-B-tris-(Cp)-borazines have been synthesized by the action of sodium cyclopenta-dienide (NaCp) on the corresponding BB'B"-trichloro-derivative,' 28c and similar reactions using Grignard reagents have afforded all ten possible B-phenyl, -methyl and -chloro substituted NN'W-trimethylborazines.' 28d While borazine derivatives are obtained in reactions of 3-butenylamine with different boranes, when the N-methylamine is used only the partially saturated heterocycle (19) is p r ~ d u c e d .' ~ ~ " In a similar vein other reactions have shown that although BH, in THF reacts with RNH and R2NH compounds to form monoaminoboranes R2NBH, it requires am-diamines amino-alcohols or glycols to react further to yield the heterocycles (20; n = 2 or 3; X = 0 S or NR; Y = 0 S or NR).129b CYMe BH x\,/y - H I Z 6 ( a ) D.R. Armstrong and D . T. Clark Theor. Chim. Acra 1972 24 307; ( b ) E. K. Mellon B. M. Coker and P. B. Dillon Inorg. Chem. 1972 11 852; (c) G. M. White-sides s. L. Regen J. B. Lisle and R. Mays J . Phys. Chem. 1972 76 2871; (4 L. D. Betowski J. J . Solomon and R. F. Porter Inorg. Chem. 1972 11 424. 12' M. A. Neiss and R. F. Porter J . Amer. Chem. SOC. 1972 94 1438. 1 2 * (a) 0. T. Beachley J . Amer. Chem. SOC. 1972,94,4223; ( b ) I. B. Atkinson D. B. Clapp, C. A. Beck and B. R. Currell J.C.S. Dalton 1972 182; (c) B. L. Therrell and E. K. Mellon Inorg. Chem. 1972,11 1137; (4 L. A. Melcher J. L. Adcock and J. J. Lagow-ski ibid.p. 1247. ( a ) H. Wille and J. Goubeau Chem. Ber. 1972 105 2157; ( b ) K. Niedenzu I. A. Boenig and E. F. Rothgery ibid. p. 2258; ( c ) A. B. Burg Inorg. Chem. 1972,11 2283 Me Me I N-/ H B, S-Me/ i2 / / N B H2 /Me Me \ R ' R2 Metal Borides. The structure of a tetragonal boron framework containing alu-minium and beryllium atoms of formula AlBeo.,B24.2 shows the Be atoms to be statistically distributed within the B, icosahedra with the A1 atoms in holes which are surrounded by a tetrahedron of four B, i~osahedra.'~' The crystal structure of W21r3B6-x (where x = 1) has been solved together with that for the compound MoIrB . In the latter there are B groups present while in the former there is a more statistical distribution of the metal Barium diboride BaB has been identified as well as BaB in mixtures of barium and boron at 1173-1 573 K ; the BaB has a hexagonal structure and can be easily hydrolysed to liberate b ~ r a n e s .' ~ ~ ' The magnetic behaviour of a series of rare-earth tetraborides (e.g. PrB is ferromagnetic SmB is antiferromagnetic and ErB is metamagnetic) has been rationalized using different indirect exchange models.133c I3O ( a ) S. G. Shore J. L. Crist B. Lockman J. R. Long and A. D. Coon J.C.S.Dalron, 1972 1123; (6) I. R. McKinley and H. Weigel J.C.S. Chem. Comm. 1972 1051 ; (c) A. Karpides and J. Graf Inorg. Nuclear Chem. Letters 1972 8 161. M. Schmidt and F. R. Rittig Z. anorg. Chem. 1972,394 152. 1 3 * K. Krogmann and H. J. Becher Z. anorg. Chem. 1972.392 197. 1 3 3 ( a ) P.Rogl F. Benesovsky and H. Nowotny Monatsh 1972,103,965; (6) K. Torkar, H. Krischner and E. Hitsch ibid. p. 744; ( c ) K. H. J. Buschow and J. H. N. Creyghton, J . Chem. Phys. 1972,57 3910 204 D. W. A . Sharp M. G. H. Wallbridge and J . H. Holloway Aluminium.-As in previous years the compounds containing aluminium-carbon bonds provide the centre of interest although several other papers have provided novel areas of chemistry. For example i.r. evidence has been presented to support the existence of an aluminium carbonyl Al,(CO), prepared by con-densing carbon monoxide and aluminium atoms in a Kr matrix at 20K.'34u The first definite evidence for the existence of an aluminium-sulphate complex has been obtained from a study of 27Al n.m.r. spectra of the [A1(H20)6]3+ ion in the presence of SO:- ions; the most likely complexes in these solutions appear to be Al(H,O),(SO,)+ together with small amounts of Al,(OH),-( H20), + .' 4b Compounds containing Al-H Bonds. The direct synthesis of alkoxyaluminium hydrides has been achieved in benzene solution at 423 K under 85 atm pressure from a mixture of Na Al MeOCH,CH,OH and H2.135a An alternative procedure is:'35b 3Na + 3NaAl(OR) + 3A1+ 6H2 -+ 2NaH + 4NaAIH(OR) + 2A1+ 3H2 2NaH + 4NaAlH(OR) + 2A1 + 3H2 -+ 6NaA1H2(OR), The thermal decomposition of complex metal hydrides such as LiAlH or KAlH, has been shown to occur through the complexes M,AlH6 although amine complexes of these hydrides MAIH,,L (where L = tertiary amine M = Li or Na) appear to be more ~ t a b 1 e .l ~ ~ ' The ether solution equilibrium LiBH + Al(BH,)3 =Li[Al(BH,),] has been studied using "B n.m.r. spectroscopy and earlier suggestions that the equilibrium is shifted towards Li[Al(BH,),] as the temperature is decreased have been confirmed.' 5d Compounds containing Al-C Bonds. The direct synthesis of some as yet un-identified organo-aluminium compounds by condensing monatomic aluminium vapour with unsaturated organic compounds (e.g. propene) at 77 K has been r e ~ 0 r t e d . l ~ ~ Organo-aluminium compounds e.g. EtAlCl have been used to catalyse the exchange between aromatics (benzene azulene etc.) and deuteriated aromatics,' 7a and for tritium labelling of organic molecules using tritiated water. 7b Exhaustive methylation (i.e. complete deoxygenation of functional groups) can be achieved using trimethylalane ; thus tertiary alcohols and ketones yield alkanes and gem-dimethyl compounds re~pectively.'~ 7c Several structures of aluminium alkyl compounds have been solved using gas-phase electron-diffraction methods.The cyclopentadienyl derivative 1 3 * ( a ) A. J . Hinchcliffe J. S. Ogden and D. D. Oswald J.C.S. Chem. Comm. 1972 338; (b) J. W. Akitt N . N. Greenwood and B. L. Khandelwal J.C.S. Dalton 1972 1226. 1 3 5 B. Casensky J. Machacek and K. Abrham ( a ) Coll. Czech. Chem. Comm. 1972 37, 1178; (b) ibid. p. 2537; ( c ) J . A. Dilts and E. C. Ashby Inorg. Chem. 1972 11 1230; (d) M. Ehemann H. Noth and G. Schmidt-Sudhoff 2. anorg. Chem. 1972 394 33. 1 3 6 P. S. Skell and L. R. Wolf J . Amer. Chem. SOC 1972 94 7919.lJ7 J. L. Garnett M. A. Long R. F. W. Vining and T. Mole ( a ) J . Amer. Chem. SOC., 1972 94 5913; (6) ibid. p. 8632; (c) A. Meisters and T. Mole J.C.S. Chem. Comm., 1972 595 The Typical Elements 205 Me,Al(C,H,) is monomeric in the gas phase and the structure suggested at present is shown in (23); it may be that the asymmetrically bonded CSH group need only act as a three-electron ligand of the n-ally1 type for the aluminium atom to complete its octet.'38a In contrast the i.r. and Raman spectra of the compound in the solid state indicate the presence of pentahapto rings of near D, sym-m e t r ~ . ' ~ ~ At 443K the hydride Me,AlH is dimeric in the vapour phase as reported last year.138c The fluoride derivative (Me,AlF) is a tetramer and appears to contain an eight-membered ring in chair-boat configuration of Cs symmetry with two of the four aluminium atoms lying in the mirror plane.'38d Other studies on Me,Al,NMe in the gas phase confirm the near tetrahedral symmetry around both the aluminium and nitrogen atoms.' 8e Several X-ray studies on aluminium alkyl derivatives have also been reported.Following an earlier study of [Na(THF),],[Me,AlC ,-,H8] the crystal structure of [Na(THF),],[Me,AlC,,H,,] has now been solved and shows a contact ion-pair complex with two cations complexed to the dimeric anion. The anion itself consists of two 1,4-dihydro-1,4-anthrylene groups fused into the anion via the Me,Al groups.' 9a The cis- and trans-isomers of (Me,AlNHMe) have been prepared by heating Me,AlNH,Me to 323 K and separating by fractional sub-limation.The solid isomers are stable in vacuum but interconvert in solution, and both decompose above 423 K to yield several products including (MeAlNMe) .139b The crystal structures of both the cis- and trans-isomers have been determined ; the former contains all the N-Me groups in the equatorial positions with the (AlN) ring in the chair configuration while for the latter the configuration at one of the N-Me groups is reversed and the (AlN) ring is now of the skew-boat type.139c Complete parameters for (AlPh,) and (Me,AlPh), both of which contain bridging phenyl groups in the solid state, have been p ~ b l i s h e d . ' ~ ~ ~ ~ ' H / \ Me Me 1 3 8 (a) D . A. Drew and A. Haaland J.C.S. Chem. Comm. 1972 1300; ( 6 ) A. Haaland and J. Weidlein J .Organometallic Chem. 1972,40 29; (c) A. Almenningen G. A. Ander-son F. R. Forgaard and A. Haaland Acta Chem. Scand. 1972 26 2315; ( d ) G. Gundersen T. Haugen and A. Haaland J.C.S. Chem. Comm. 1972 708; (e) G. A. Anderson F. R. Forgaard and A. Haaland Acta Chem. Scand. 1972 26 1947. 139 (a) D. J. Brauer and G. D. Stucky J . Organometallic Chem. 1972 37 217; (b) K . J . Alford K. Gosling and J. D. Smith J.C.S. Dalton 1972,2203 ; ( c ) G. M. McLaughlin, G. A. Sim and J. D. Smith ibid. p. 2197; J. M. Malone and W. S. McDonald (d) ibid., p. 2646; ( e ) ibid. p. 2649 206 D. W. A . Sharp M . G. H. Wallbridge and J. H. Holloway The exchange of methyl groups in mixtures such as Al,Me,-GaMe, A12Me6-ZnMe, and Al,Me,-AlMe ,B (where B = pyridine THF etc.) has been studied using 'H n.m.r.spectroscopy. In general the kinetics follow the simple first-order dissociative or second-order associative rate law but in Al,Me,-AlMe ,CSH,N exchange the process probably contains contributions from both pathways. When the base involves a Group VI donor atom a base-assisted associative exchange mechanism is proposed involving interaction of the second lone pair on the donor atom with A1,Me,.'40" New values for the heats of dissociation of liquid and gaseous trimethyl- and triethyl-alane have been obtained and are different from previously reported values being typically 81.5 kJ (mol dimer)-for liquid and gaseous A12Me6 and 71.0 and 76.4kJ (mol dimer)-' for liquid and gaseous Al&t, respectively.'40b A variety of reactions involving organo-aluminium compounds have been reported.The crystal structure of one of the transition-metal complexes reported last year [(n-CSH,)W(C0)3A1Mez]z is shown schematically in (24) ; the twelve-membered ring is slightly puckered with approximate octahedral and tetrahedral co-ordination around the tungsten and aluminium atoms re~pectively.'~~" Interaction between bridging carbonyl groups in [(C,H,)Fe(CO),] [(C,H,)-Ru(CO),], and [(C,H,)Mo(CO),] and AlEt has been inferred from an i.r. study of the solutions,141b and simple Mo-CO-Al(Ga) bridges are also apparently formed when Mo(phen)(PPh,),(CO) (phen = o-phenanthroline) is mixed with AlEt, AlBu; or GaMe .l4lC The relative base strengths of a series of dinitrogen and carbonyl complexes towards AlMe in benzene solution have been determined using 'H n.m.r.spectroscopy the results indicating a decrease in the order THF > trans-ReClN,(PMe,Ph) > trans-Mo(N,),(dpe) > trans-W(N,),(dpe) > mer-OsCl,N,(PEt Ph) (where dpe = Ph ,PCH ,CH PPh,).'4' Trimethylalane has been found to-react with (C,H,),ZrH to yield the hydrogen-bridged compound (25). ' 4' = H / \ \ / (C H ,) Zr( HAlMe,) (Me AlH)Zr(C H& H (25) The gas-phase thermal reaction of monomeric AlMe molecules with ethylene has been studied over the temperature range 455-549 K. The reaction scheme can be summarized as : 14" ( a ) T. L. Brown and L. L. Murrell J. Amer. Chem. SOC. 1972,94 378; (b) M. B. Smith, J. Organometallic Chem. 1972 46 3 1 . 14' ( a ) G. J. Gainsford R. R. Schrieke and J . D. Smith J.C.S.Chem. Comm. 1972 650; (6) A. Alick N . J. Nelson D. Strope and D. F. Shriver Znorg. Chem. 1972 1 1 2976; ( c ) D. F. Shriver and A. Alick ibid. p. 2984; (6) J. Chatt R. H. Crabtree and R. L. Richards J.C.S. Chem. Comm. 1972 534; ( e ) P. C. Wailes H. Weigold and A. P. Bell, J . Organometallic Chem. 1972 43 C29 The Typical Elements 207 Me,Al + C2H4 -+ Me,Al-CH,-CH,-CH -@-+ Me,AlH + CH,=CHCH, &A Me,AlC,H, The kinetic results cannot be rationalized in terms of the often quoted simple quadrupolar four-centre transition state and instead an intermediate involving the olefin co-ordinatively bonded to the aluminium atom is p r ~ p o s e d . ' ~ ~ " The essential presence of an AlR fragment not co-ordinated with any ligand has also been demonstrated from a kinetic study of AlEt with oct-1-ene in diphenyl ether.142b The presence of trialkylalanes has been found to catalyse the addition of HCN to a-enones through the intermediate formation of R,AlCN com-pounds. 142c Studies on co-ordination compounds derived from organo-aluminium compounds include a ' H n.m.r. examination of various vinyl compounds, including (C,H,),M,NMe (M = Al Ga or In),1430 and of adducts formed from AlEt or Et,AlCl and ditertiary phosphines [Ph,P(CH,),PPh, where n = 1,2,3, 4 or 6].143b The synthesis of Et,AlI,NHMe, which is monomeric in benzene, has been reported from mixing AlEt with the salt Me,NH,+I-; heating the adduct to 413 K liberates ethane while Et(I)AlNMe is formed.143c The cyclic compound Al,Me,(NMe,),H reacts with trimethylamine in two ways ; when the aluminium compound is not very pure (Me,AlNMe,) and Me,AlH,NMe, are formed whereas with pure material Al,Me,(NMe,),H and Me,AlH,NMe, are formed.'43d With oxygen as the ligand donor atom a series of acetylacetone (acac) complexes have been prepared by the action of acac on Me,Al Me,AlCl, or MeAlCl, with the formulae Me,Al(acac) (acac)AlCl, and Me(Cl)Al(a~ac),'~~" and a series of quinolinolato-complexes of the type R,MQ (R = Me Et or Bu' ; M = Al Ga or In; Q = anion of quinolin-8-01) has been prepared.144b Lead oxide PbO is alkylated to yield PbMe and (Me,Al),O when heated with tri-methylalane at 408 K,14,' and the formation of a Group IIIB-tin bond results from the action of LiSnMe on a metal alkyl to yield Li(Me,SnMMe,) (M = Al, Ga In or Tl) although the aluminium compound is the least stable and de-composes after 24 h to a mixture of LiAlMe, SnMe, and Li[Sn(SnMe,),].'44d An Al-S(or P)-Ni linkage is said to result from the reaction: 14' ( a ) K.W. Egger and A. T. Cocks J . Amer. Chem. SOC. 1972 94 1810; (6) P. E. M. Allen A. E. Byers and R. M. Lough J.C.S. Dalton 1972 479; ( c ) W. Nagata M. Yoshioka and S. Hirai J . Amer. Chem. Soc. 1972 94 4635. 1 4 3 ( a ) H. D. Visser and J. P. Oliver J . Organometallic Chem. 1972 40 7; (6) T. Kegawa and H. Hashimoto Bull. Chem. SOC. Japan 1972 45 1739; ( c ) K. Gosling and A. L. Bhuiyan Inorg. Nuclear Chem. Letters 1972,8 329; ( d ) J. D. Glore and E. P. Schram, Inorg. Chem. 1972 11 1532. 144 ( a ) S. Pacynkiewicz and K. Dowbar J. Organometallic Chem.1972,43 75; (b) B. Sen, G. L. White and J. D. Wander J.C.S. Dalton ( c ) M. Boleslawski and S. Pacynkiewicz, J. Organometallic Chem. 1972,43,8 1 ; (d) A. T. Weibel and J. P. Oliver J . Amer. Chem. SOC. 1972 94 8590; ( e ) T. Hirabayashi and Y . Ishii J . Organometallic Chem. 1972, 39 C85 208 D. W. A . Sharp M . G. H . Wallbridge and J. H. Holloway (R,AlX) + Ni(cod) -+ (R,AlX),Ni(cod) + cod (R = Me,X = SMe;R = Me,X = SPh; R = Et,X = PPh,; cod = cyclo-octadiene) However little experimental evidence is given for such a conclusion and further results are required.',,' Compounds containing Al-0 Bonds. In a continuing study of stereochemically non-rigid molecules the crystal structure of tris(tropolonato)aluminium(III) shows the ligands to be slightly bent in the vicinity of the metal atom but the most significant feature of the AlO co-ordination sphere is the 48.1" twist angle compared with 60" for a regular octahedron.For this molecule the non-rigidity possibly lies in the ground-state geometry of the complex and the distortion around the metal atom towards trigonal prismatic probably offers a relatively low-energy pathway to rearrangement through a twisting about the three-fold axis of the chelate molecule.145" Double isopropoxides M[M'(OPr'),] (M,M' = Al Ga or In) containing bridging alkoxy-groups between the metal atoms are volatile compounds which have been prepared by treating the anhydrous metal chloride of one metal with the potassium salt KM(OPr') of another metal.145b The use of 'H n.m.r. spectroscopy has shown that when AlI'' Ga"' or In"' ions are dissolved in trimethyl phosphite-water mixtures a total of six solvent molecules fill the first co-ordination sphere around the metal ion but that several species Al[P(OMe),],-,(H,O) are believed to co-exist in equilibrium in solution.14" Rapid ring-opening of THF occurs when triethylborane is added to Li[Al(OBu*),] yielding 1-butanol but in the absence of the boron alkyl no reaction Compounds containing Aluminium-Halogen Bonds. The existence of solvated halides MX (M = B Al or Ga) in acetonitrile has been established from 'H n.m.r. spectra; for BX and GaX the solvation number of one suggests the presence of [MX,(MeCN),] + MX,- species while for AlX the solution appears to contain [A1(M&N),]3 + [AlCl,-1 ions corresponding to a solvation number of 1S.146a Another study using "A1 n.m.r.spectra shows that all five mixed halide ions AlCl,Br,- (0 < n < 4) exist in equilibrium in acetonitrile solution!46b The solid-state structures of a series of 1 1 adducts between MCl (M = Al, Ga In or T1) and 2,2',2"-terpyridyl (terpy) show that the Al In and T. compounds form an isomorphous series and although their structures could not be unam-biguously determined from the i.r. spectra it does appear that the gallium complex 14' (a) E. L. Muetterties and L. J . Guggenberger J. Amer. Chem. SOC. 1972 94 8046; (b) A. Mehrotra and R. C. Mehrotra Inorg. Chem. 1972,11,2170; ( c ) J. Crea and S. F. Lincoln ibid. p. 1131 ; ( d ) H. C. Brown S. Krishnamurthy and R. A. Coleman J . Amer. Chem.SOC. 1972 94 1750. ' 4 6 (a) I . Y . Ahmed and C. D. Schmulbach Inorg. Chem. 1972,11,228; (b) D . E. H. Jones, J.C.S. Dalton 1972 567; (c) G. Beran K. Dymock H. A. Patel A. J. Carty and P. M. Boorman Inorg. Chem. 1972 11 896 The Typical Elements 209 has a distorted octahedral trans-configuration.' The crystal structures of Hg,(AlCl,) ,147a Te4(AlCl4), and Te4(A1,C17),'47b have been determined by X-ray methods ; the mercury compound contains discrete molecules having a nearly linear C1-Hg-Hg-Hg-C1 skeleton with the chlorine atoms being shared with two nearly tetrahedral AICl,- anions. The tellurium compounds contain square Te42+ ions and tetrahedral AlCl,- or Cl3A1-Cl-AIC1,- anions. The 1 1 adduct A1Cl3,S4N has been and an interesting study of the interaction of AlBr and All with graphite shows that unlike the chloride, AlBr reacts only if free bromine is also present and then a compound C,,AIBr,Bro, has been is01ated.l~~' The resistivity of a range of such compounds suggests that the bromine plays a large part in assisting charge-transfer processes.148c The concentration dependence of the specific conductivity of AlCl and LiAlH in tetrahydrofuran has been suggested to arise from the formation of AIHCl, AlH,Cl and the ionized complexes Li'AlHC1,- and LifAlH2C12-.149" A new dye Mordant Blue 31 has been found to be a satis-factory reagent for the fluorometric determination of aluminium and gallium since it forms 1 1 complexes with these metals in acidic solution.'49b Although the possibility of any A1-H-A1 species is not discussed another study shows that when associated compounds such as Bu,'AlH and Bu,'AICl are mixed then signals arising from mixed complexes which may be either dimeric or trimeric, can be detected in the 'H n.m.r.spectra of mixtures of these two corn pound^.'^^^ Gallium and Indium-The investigations on these two elements follow a similar pattern to those in previous years. The halogeno-compounds and co-ordination chemistry continue to be of interest and compounds containing metal-carbon bonds also form the basis of many papers. Compounds containing Metal-Hydrogen Bonds. A series of cyclogallazanes [CH,-(CH,),-$+I-GaH,] (x = 1 2 3 or 4; n = 2 or 3) together with the analogous boron and aluminium compounds have been prepared by the action of the base on the Me,N,MH (M = B Al or Ga) compounds and the factors affecting the ring size in this series of compounds have been surnmari~ed.'~~" The details of the crystal structure of the aziridinylgallane trimer have been reported.' 50b Compounds containing Metal-Carbon and Metal-Halogen Bonds.The crystal structure of tris(cyclopentadienyl)indium(m) reveals that the molecule is arranged in infinite polymeric chains with each chain unit composed of an indium atom linked to two terminal a-bonded and two bridging cyclopentadienyl groups. 14' ( a ) R . D. Ellison H . A. Levy and K. W. Fung Inorg. Chem. 1972,11 833; ( 6 ) T. W. Couch D. A. Lokken and J . D. Corbett ibid. p. 357. 1 4 * ( a ) F. P. Olsen Inorg. Chem. 1972 11 2836; T. Sasa Y. Takahashi and T. Mukaibo, ( 6 ) Bull.Chem. Soc. Japan 1972,45 937; ( c ) ibid. p. 2657. 149 ( a ) M. Yoshio N. Ishibashi H. Waki and T. Seiyama J. Inorg. Nuclear Chem. 1972, 34 2439; ( b ) K. Hiraki Bull. Chem. Soc. Japan 1972 45 789; ( c ) J. J. Eisch and S. G. Rhee J . Organometallic Chem. 1972 38 C25. Is' ( a ) A. Storr B. S. Thomas and A. D. Penland J.C.S. Dalton 1972 326; ( b ) W. Harrison A. Storr and J . Trotter ibid. p. 1554 2 10 D. W. A . Sharp M . G. H. Wallbridge and J. H . Holloway These four groups give a slightly distorted tetrahedral environment around each metal atom and provide the first clear evidence for the existence of a bridging cyclopentadienyl group.' 5 1 a The crystal structures of the salts MInMe (M = Li, Na K Rb or Cs) also show a tetrahedral array of methyl groups around each indium atom and each alkali-metal cation is in turn surrounded by four methyl groups in a similar orientation.' ' A series of monomeric four-co-ordinate complexes (C6F,),In,L[L = C5H5N Ph3P Ph3P0 Ph3As0 or tmed (NNN'N'-tetramethylethylenediamine)] and five-co-ordinate complexes (C,F,),In,L, (L = Me,SO or THF) have been prepared and other complexes [(C,F,)In],L [L = bipyridyl or Ph,P(CH,),PPh,] together with the (C,F,),In(tmed) com-pounds are considered to contain bridging ligands with a four- and five-co-ordinate indium atom respectively.' l C The gallium halides Ga,X (X = C1 Br or I) react with primary secondary, and tertiary alkyl halides although the ease with which the various reactions proceed depends upon the combination of groups used.However typical compounds isolated include RGa,Br (R = Me or Et),15" MeGa,Cl,I and MeGa,Br,I.152b Gallium (and indium) metal will also react with RX compounds (R = Me or Et ; X = Br or I) at room temperature to yield R3Ga,X3 which may be considered as a mixture of R,GaX and RGaX .' 52c A series of indium com-pounds of empirical formula RInX (X = Br or I ; R = Me Et Pr or Bu) has been synthesized from the action of InBr and In1 with the corresponding alkyl halide, and spectroscopic evidence suggests that the bromo-compounds are probably polymeric while the iodides are best formulated as InMe,' InI,-.'52d The interaction of a series of R,InX or MeInC1 compounds with Me3SbS affords stibonium salts such as RMe3SbX (R = Me or Et ; X = C1 Br or I) and Me,SbCl respectively while with the trichloride InCl the intermediate 1 1 adduct (which contains an In-S bond) reacts further to produce Me3SbC1 .152e Dealkylation of indium alkyl compounds occurs on reaction with various ligands such as a-mononitroalkanes,' 5 2 f SSCNMe (dtc) 8-hydroxyquinoline (oxH) and HOC,H,NMe ' 52g and the corresponding dialkylindium compounds Et,In[C(NO,)R,] (R = H or Me) Me,In(dtc) MeIn(dtc) Et,In(ox) and R,InOC,H,NMe (R = Me or Et) are obtained.The hydrolysis of the Innr ion in solutions containing chloride ions is in fact concerned with ions such as InC12+ and InC12+,153a and following estimates of the [In3+] concentration as a function of [Cl-] it has been suggested that only a small part of the indium chloride complexes can be hydrolysed before the main l s l (a) F.W. B. Einstein M. M. Gilbert and D. G. Tuck Inorg. Chem. 1972 11 2832; ( 6 ) K. Hoffmann and E. Weiss J . Organometallic Chem. 1972,37 1 ; (c) G. B. Deacon and J. C. Parrott Austral. J . Chem. 1972 25 1169. I s 2 W. Lind and I. J. Worrall ( a ) J . Organometallic Chem. 1972 36 3 5 ; ( 6 ) ibid. p. 35; M . J. S. Gynane L. G. Waterworth and I. J . Worrall ( c ) ibid. p. C59; ( d ) ibid. p. 257; ( e ) T. Maeda G . Yoshida and R. Okawara ibid. l972,44,237;(f) L. M. Golubinskaya, V. I . Bregadze E. V. Bryuchova V. I . Svergun G. K. Semin and 0. Yu. Okhlobystin, ibid. 1972 40 275; ( g ) T. Maeda and R. Okawara ibid. 1972,39 87. 1 5 3 D. Ferri ( a ) Acfa Chem. Scand. 1972 26 733; ( 6 ) ibid. p. 747; ( c ) S. F. Lincoln A. Sandercock and D. R. Stranks J.C.S. Chem.Comm. 1972 1069; ( d ) H. A. Oye and W. Bues Inorg. Nuclear Chem. Letters 1972 8 31 The Typical Elements 21 1 product of hydrolysis In2C10H4+ is pre~ipitated.’’~~ The rate parameters of the exchange of a C1- ion on GaC1,- in concentrated hydrochloric acid have been obtained from ,’Cl magnetic resonance results by following the broadening of the resonance absorption,153c and in addition to the GaC1,- and Ga,Cl,-ions the neutral dimer Ga,Cl has been identified in mixtures of CsCl and GaCl,.153d The I ~ I C ~ ~ - ion has been identified in the crystal structure of (MeNH,),InCI and in lower oxidation state indium compounds such as InBr and In,Br the ionic formulations In+ (InBr4-) and 2(1n+) In,Br,’-, respectively have been proposed from the Raman spectra of the solids.154b Force-constant calculations have been made on several anionic In’ and In”’ halide complexes namely InX,,- (X = C1 Br or I) InX,- (X = C1 Br or I), InCl,,- and InCl, - and for the In”’ chloro-anions the constant decreases linearly with increasing co-ordination number.Significant ionic character in the In-X bonds is suggested from the way in which the constant varies with the electronegativity of the ligand the co-ordination number and oxidation state of the metal When gallium trichloride reacts with S,O,F or BrOS0,F the tris-fluorosulphate Ga(SO,F) is obtained and the i.r. spectrum suggests that the compound is polymeric containing bridging bidentate fluorosulphate groups about a six-co-ordinate metal atom.’” The crystal structure of GaCI,,-bipy (bipy = 2,2’-bipyridyl) shows the presence of the [cis-Cl,Ga(bipy),]+ GaC1,- ions,’ and the first hydroxo-bridged octahedral gallium chloride complex (26) which has been characterized from X-ray data is formed in the attempted preparation of GaCI,(MeMe’dpma) [MeMe’dpma = methyL(6-methyl-2-pyridylmethyl)(2-pyridylmethyl)amine] when the reaction solution is hydrolysed by moist acetonitrile.In the absence of moisture a different complex is obtained which is formulated as [GaCI,(MeMe’dpma)]+ GaC1,- or [GaCl,-(MeMe’dpma)] [GaCl,] and with InCl or TICl the non-ionic compounds MCl,(MeMe’dpma) are The formation of 1 1 adducts between M’’(saen) [saen = NN’-ethylenebis(salicy1ideneaminato) ; M = Co Ni or Cu] and InX (X = C1 or Br) has been reported and although the planarity about M is preserved in the complex the question of whether M is five-co-ordinate or not could not be res~lved.’’~~ Compounds containing Gallium (and Indium)-Transition Metal Bonds and Mis-cellaneous Studies.The red crystalline compound Ga,[Mn(CO),] has been prepared by heating gallium metal with Mn,(CO), in a sealed tube at 413 K, and i.r. and Raman studies indicate the presence of a Mn-Ga-Ga-Mn, skeleton but for the In[Mn(CO),] compound prepared similarly the framework ( a ) H. Schlimper and M . L. Ziegler Z . Naturforsch. 1972,27b 377; ( b ) L. Waterworth and I . J. Worrall Inorg. Nuclear Chem. Letters. 1972 8 123; (c) J. G. Contreras and D. G . Tuck Inorg. Chem. 1972 11 2967. I s 5 A. Storr P. A. Yeats and F. Aubke Canad. J. Chem. 1972 50 452. 1 5 6 ( a ) R.Restivo and G. J. Palenik J.C.S. Dalton 1972 341; (b) K. Dymock G. J. Palenik and A. J. Carty J.C.S. Chem. Comm. 1972 1218; ( c ) M. D. Hobday and T. D. Smith J.C.S. Dalton 1972 2287 212 D. W. A . Sharp M. G. H. Wallbridge and J . H. Holloway Me uCH2 / .Me (26) consists of a planar InMn skeleton.'57a The In-Mn bonds in In[Mn(CO),], are easily cleaved by halogens or hydrogen halides to form the halogeno-deriva-tives X -,In[Mn(CO),] (X = C1 or Br ; n = 1 or 2) and while these compounds undergo disproportionation reactions in acetone or methanol to yield In[Mn(CO),] and InX, in acetonitrile they are converted into the [(MeCN),-InMn,(CO),,] + cation.' 5 7 b A general method for preparing transition metal-indium bonds has been devised as typified by the example '' 3Naf[C,H,(CO),Mo]- + InCl -+ In[Mo(CO),C,H,] + 3NaCl The formation constants for a series of mixed metal complexes between In"' and U'" with malic tartaric and citric acids have been determined and for the first two acids the equilibrium can be written as U022+ + In3+ + 2 H 3 L e UO,InL,- + 6H+ the logarithms of the equilibrium constants being - 7.62 and -7.14 for the malate and tartrate systems respectively.For citric acid the equilibrium is UOZ2+ + In3+ + 2H4L~U0,1nL,3- + SH' where two of the protons arise from the hydroxy-groups of the ligand. It is worthwhile noting that there is only limited information available on mixed metal systems compared with that published on mixed ligand systems.' 5 8 n Stability constants have been determined using conventional potentiometric techniques for the interaction of In'" with RCOCH,COCF (R = 2-furyl 2-thienyl C,H, 2-naphthyl Bu' or and the polarographic behaviour of In"' in several nitrates has been examined ; the results have been interpreted with respect to viscosity diffusion coefficients and ionic solvation parameters.58c The crystal structure of Bi,In4S9 has been determined the sulphur atoms forming a close-packed arrangement with three indium atoms being octahedrally surrounded by sulphur atoms and the fourth indium atom being in a distorted tetrahedron of sulphur atoms. The six- and seven-co-ordination of the two bismuth atoms by sulphur is related to the co-ordination in Bi2S .159 15' ( a ) H. J . Haupt and F. Neumann Z . anorg. Chem. 1972 394 67; A. T. T.Hsieh and M . J . Mays (b) J.C.S. Dalton 1972 516; ( c ) J . Organometallic Chem. 1972 37 9. ( a ) G. Markovits P. Klotz and L. Newman Inorg. Chem. 1972 11 2405; (6) K. Bowden G. M. Tanner and D. G. Tuck Canad. J . Chem. 1972 50 2622; ( c ) P. S. Jain and S. Lal Monarsh 1972 103 751. I s 9 G . Chapius C. Gnehm and V. Kramer Acta Cryst. 1972 B28 3128 The TypicaI Elements 213 Thallium-The 2o 5Tl-'H spin-spin coupling constants have been measured for a series of arylthallium dichlorides and while they are similar to the 'H-IH constants in benzenes they are of course much larger and therefore easier to measure.' 60a A number of aryl(chloromethy1)thallium chlorides Ar(ClCH,)TlCl (Ar = C6H5 or p-Me*C&) have been prepared by the action of diazomethane on ArTlCI compounds,'60b and complexes Of C6H5TlC12 with several terdentate (with ON0 and ONS as ligand atoms) and quadridentate ligands (with ONNO as ligand atoms) have been characterized.'60' The crystal structure of TlCl ,-(1,lO-phenanthroline) shows the metal atom to be in a distorted octahedral environment the basal plane being formed by the ligand and two chlorine atoms with another two chlorine atoms at the apices the whole molecule existing as a weakly bonded dimeric species.' 60d In the structure of salicylato-( 1,lO-phen-anthroline)thallium(I) shown schematically in (27) the two halves of the dimeric molecule are related by a two-fold axis while the five atoms in the metal co-ordination sphere form the base of a shallow irregular pentagonal pyramid which has the metal atom at its apex.161Q Another series of Tl' compkes has been prepared by dissolving TlL compounds (themselves prepared by dissolving TlOH in HL) in the acid HL where L is a potential bidentate ligand such as 8-hydroxyquinoline 2-ni trophenol or 2-hydroxybenzoic acid and in comparison with similar potassium complexes the thallium compounds are rather more stable.I6 l b The thallium(1) hexafluorogermanate Tl,GeF6 prepared from the action of a Ge0,-HF mixture on thallium(:) acetate has a similar structure to K2GeF6,l6," and other structure determinations on T10F'62b and T1F,'62' show that the former is related to the fluorite structure but with thallium atoms in the distorted eight-fold co-ordination site while in the latter each metal atom has eight nearest neighbours arranged in a distorted trigonal prism with two fluorine atoms above the side faces of the prism.The kinetics of the reduction of Tl"' ions by As"' ions in aqueous perchloric acid forming T1' and As" ions have been recorded; the reactive species are T10H2 + and HAsO .163a The photolytic destruction of luminescence of T1' solutions containing chloride ions has been found to be caused by an oxidation process T1' + 2H+ + 0 +T1"' + H,O, for which the presence of chloride ions is necessary. ' 63b 160 (a) J . P. Maher M. Evans and M. Harrison J.C.S. Dalton 1972 188; (b) T. Abe and R. Okawara J. Organometallic Chem. 1972,43 117; ( c ) L. Pellerito R. Cefalu and G. Ruisi ibid. 1972 44 243; (4 W. J . Baxter and G. Gafner Inorg. Chem. 1972 11 176. 16' (a) D.L. Hughes and M. R. Truter J.C.S. Dalton 1972 2214; (b) N. S. Poonia and M. R. Truter ibid. p. 1791. 16' ( a ) B. Hajek and F. Benda Cull. Czech. Chem. Comm. 1972 37 2534; (b) M. Vlasse, J. Grannec and J. Portier Acta Cryst. 1972 B28 3426; (c) C. H. Hebecker Z . anorg. Chem. 1972,393 223. 1 6 3 (a) P. D. Sharma and V. K. Gupta J.C.S. Dalton 1972 52; (b) G. F. Kirkbright P. J. Mayne and T. S. West ibid. p. 19 18 214 D. W. A . Sharp M. G. H . Wallbridge and J. H . Holloway >-0 / N \ / - 5 PART II Groups IV and V 1 GroupIV Carbon.-A considerable amount of work continues to be carried out on graphite intercalation compounds and the compounds with alkali metals have been reviewed.'" Amongst substances that can be intercalated into graphite are mixed halogens (iodine is inactive on its own but is intercalated in the presence of other halogens") hydrogen fluoride," and hexachloroplatinic acid (PtCl is inactive).lc The intercalates between tripositive halides and graphite are good metallic conductors comparable with nickel or iron.ld Intercalation compounds of the alkali metals show possibility for their purification ;le graphite-potassium is an active catalyst for deuterium-paraffin exchange ;lJ the graphite-FeC1,-K system exhibits high catalytic activity for the synthesis of ammonia,Ig and the graphite-PdC1,-Na system forms dimethyl ether from hydrogen and carbon monoxide.lh Methyl and ethyl hexafluoroantimonates and their SbF adducts are stable in SbF,-S02 or SbF,-SO,ClF solutions at low temperatures. There appears to be a fluorine bridge between the alkyl group and antimony and even at 150 K there is rapid alkyl-group exchange.2 The detailed structures of several carbonium ions are now known ; in azidoformamidium chloride [(H,N),CN,]Cl the (H,N),C (a) Y.N. Novikov and M. E. Vol'pin Run. Chem. Rev. 1971 9 733; (6) G. Furdin and A. Herold Bull. SOC. chim. France 1972 1768 3345; ( c ) A. A. Opaloroskii A. S. Nazarov and A. A. Uminskii Russ. J. Inorg. Chem. 1972 17 632; A. Boeck and W. Rudorff Z. anorg. Chem. 1972 392 236; (6) B. Bach and A. R. Ubbelohde J. Chem. SOC. ( A ) 1971 3669; ( e ) D. Billaud and A. Herold Bull. SOC. chim. France, 1972 103; (f) M. Ichikawa K. Kawase and K. Tamaru J.C.S. Chem. Comm. 1972, 177; ( g ) M. Ichikawa T. Kondo K. Kawase M. Sudo T.Onishi and K. Tamaru, ibid. p. 176; ( h ) S. Naito 0. Ogawa M. Ichikawa and K. Tamaru ibid. p. 1266. J. Bacon and R. J. Gillespie J. Amer. Chem. SOC. 1971 93 6914 The Typical Elements 215 and N parts of the cation belong to almost independent n-bonding system^.^ Simultaneous deposition of beams of lithium and methyl halides gives halogeno-methyl radicals (e.g. CH,Br') ; the radicals appear to have nearly planar ge~metries.~ The carbanion in Li(Me,NCH,CH,NMe,)CPh does not quite have a planar arrangement about the central carbon atom but there appears to be interaction between the lithium and one phenyl ring," and similar interaction is found in other lithium derivatives of car bani on^.^' The anions in dinitromethanides are generally planar about the central carbon atom but the nitro-groups are some-times propeller-shaped [in K NCC(NO,),]S' and sometimes twisted asymmetric-ally [in Rb NCC(N02)2Sd and K P-C~C~H~C(NO,),].~~ Rb2(02N)2C2(N02)2 has a slightly distorted anion because of steric effects but the arrangement about each carbon atom is still planar.'/ There continues to be a considerable interest in pseudohalogen derivatives related to cyanides.The hydrolysis of cyanide ion in aqueous solution involves attack of OH- on HCN.6" Cyanogen azide is an explosive oil obtained from sodium azide and cyanogen chloride in anhydrous media ; it undergoes an exten-sive series of organic reactions.6b Azodicarbonitrile NCNzNCN is best formed from cyanogen chloride hydrazine hydrate and sodium a ~ i d e . ~ " It is an orange-red solid with a trans c~nfiguration.~' The microwave spectrum of ClNCO confirms that it is an isocyanate ; it is a planar bent molecule and the isocyanate group is bent at carbon away from the chlorine.8" Me,SiNCO and Me,CNCO appear to have linear MNCO chains8' (see also pp.225 and 244). Bromine isocyan-ate briefly reported last year,8c may be prepared by heating tribromoisocyanate.8d The (SCN) - ion is formed transitorily on oxidizing NH,SCN in acetonitrile.' Methyl allophanate is observed in its stable diprotonated form [isomers of H,N=C(OH)*NH=C(OH)OMe] in FSO,H-SbF,-SO,. l o Trichloroyethyl isocyanide dichloride Cl,CN=CCI, reacts with HCl-SbC15 to give CI,CN(H)= CCl SbCl,- which eliminates HCl to give the formamidium salt Cl,CN= CCl,SbCl .' l a Enamines react with inorganic halides to give organometallic derivatives e.g.SiC1 + H,C=C(NMe,)Ph base Cl,SiCH=C(NMe,)Ph in a + + 3 4 5 6 7 8 9 10 1 1 H . Henke and H. Barnighausen Acta Cryst. 1972 B28 1100. D. W. Smith and L. Andrews J . Chem. Phys. 1971 55 5295;'J. I. Raymond and L. Andrews J . Phys. Chem. 1971 75 3235. ( a ) J. J. Brooks and G. D. Stucky J . Amer. Chem. SOC. 1972,94,7333; ( b ) J. J. Brooks, W. Rhine and G. D. Stucky ibid. pp. 7339 7346; (c) B. Klewe Acta Chem. Scand., 1972 26 1921 ; (6) H. J. Bjernstad and B. Klewe ibid. p. 1874; ( e ) B. Klewe and S. Ramsoy ibid. p. 1058; (f) B. Klewe ibid. p. 1049. ( a ) G. H. Wiegand and M. Tremelling J . Org. Chem. 1972,37 914; ( b ) F. D. Marsh, ibid. p. 2966. ( a ) B. Bak R. Eskildsen and P. Jansen Acta Chem.Scand. 1971,25 3181; ( b ) B. Bak and P. Jansen J . Mol. Structure 1972 11 25. ( a ) W. H. Hocking and M. C. L. Gerry J . Mol. Spectroscopy 1972 42 547; ( b ) A. J . Careless M. C. Green and H. W. Kroto Chem. Phys. Letters 1972 16 414; M. Winewasser ibid. 1971 11 515; ( c ) D. W. A. Sharp M. G. H. Wallbridge and J. H. Holloway Ann. Reports 1971 68 A 295; (d) W. Gottardi Monatsh. 1972,103 1150. G. Cauquis and G. Pierre Bull. SOC. chim. France 1972 2244. G . A. Olah A. T. Ku and J. A. Olah J . Org. Chem. 1971,36 3582. ( a ) A. Schmidt Chem. Ber. 1972 105 3050; ( 6 ) H. Weingarten and J. S. Wager, Synth. Znorg. Metal-org. Chem. 1971 1 123 216 D. W. A . Sharp M. G. H . Wallbridge and J. H. Holloway general reaction which should be capable of much extension; amidium salts e.g.CI,GeCMe,C(NMe,) C1- are formed as intermediates. ' ' Dimethylcarbodi-imide MeNCNMe is prepared by desulphurizing NN'-dimethylthiourea with mercury(r1) oxide ; it undergoes spontaneous cyclic trimerization to hexamethyl-isomelamine.' Carbodi-imide derivatives e.g. R,Si(NCNPh) are readily formed from the corresponding cyanamide e.g. PhNCNH and the appropriate halide ;' 2 b N ?'-dicyclohexylcarbodi-imide can be alkylated to a carbodi-imidium cation R 'R2N=C=NR'. ' 2c Trifluoromethylsulphenyl chloride CF,SCI reacts with cyanamides by HCl elimination and addition to the multiple bond to give, for example (CF,S),NC(Cl)=NSCF from H,NCN ; cyanides are formed on heating e.g. CF,SN(Me)C(Cl)NSCF gives CF,SN(Me)CN and these can be hydrolysed to substituted ureas.', Alkyl carbamates in strong acid solutions at low temperatures are exclusively 0-protonated although rearrangements to N-protonated species occur on warm-ing.14 Methyl hydrogen carbonate MeHCO, is formed by the reaction of Na[MeOCO,] (from NaOMe and CO in methanol) with hydrogen chloride.' 5a Silyl-carbamates -carbonates and -thiocarbonates e.g. R,NC(O)OSiMe, are prepared from salts and the chlorosilane ;' '' bis(sily1)carbonates result when silanes react with carbonates in the presence of nickel catalysts.' 5 c Polymeric cyanodithioformic acid [NCCS( SH)] is formed on acidification of the sodium salt ;16a trimeric [HCS(SH)] is formed similarly from KHCS but the monomer and dimer are present in the gas phase and in chlorocarbon Esters [HCS(SR)] are formed from the potassium salt and alkyl iodides; they interact with thiols to give orthoesters HC(SR) .I6' Chloroform and potassium sulphide react to give the dithioformate KHCS ; other salts have been prepared from the free acid and alkoxides.'6d A platinum derivative of a fluorodithioformic acid, [(Ph,P),PtS,CF]+[HF,]- is formed by CS insertion into a Pt-F bond.16e Lithium trithiocarbonate Li,CS3 is best formed from butyl-lithium and the free acid.'' Spectroscopic studies on carbon monoxide in inert matrices suggest the presence of aggregates of CO molecules. Carbon atoms and carbon-containing molecules can react in matrices to give new species. Photolysis of l 2 ( a ) G. Rapi G. Sbrana and N. Gelsomini J . Chem. SOC. (0 1971 3827; ( 6 ) H. Kohler and H.V. Dohler Z . anorg. Chem. 1971 386 197; (c) R. Scheffold and E. Saladin Angew. Chem. Internat. Edn. 1972 11 229. l 3 A. Haas and V. Plass Chem. Ber. 1972 105 2047. l 4 G. A. Olah A. M. White and A. T. Ku J . Org. Chem. 1971 36 3585. I s ( a ) G. Gattow and W. Behrendt Angew. Chem. Internat. Edn. 1972 11 534; (b) Y. Yamamoto and D. S. Tarbell J . Org. Chem. 1971 36 2954; L. Birkofer and P. Sommer J . Organometallic Chem. 1972 35 C15; (c) M. Paul J. Dunogues R. Calas, and E. Frainnet ibid. 1972 38 267. I b ( a ) R. Engler and G. Gattow Z . anorg. Chem. 1972 390 73; ( 6 ) R. Engler and G. Gattow ibid. 1972 389 145; ( c ) R. Engler G. Gattow and M. Drager ibid. 1972, 390,64; (d) R. Engler G. Gattow and M. Drager ibid. 1972,388,229; ( e ) J. A. Evans, M. J. Hacker R.D. W. Kemmitt D. R. Russell and J. Stocks J.C.S. Chem. Comm., 1972 72. H. Seidel and R. Meyn Z . Narurforsch. 1971 26b 1192. ( a ) J . B. Davies and H. E. Hallam J.C.S. Faraday I I 1972 509; ( 6 ) R. L. deKock and W. Weltner jun. J . Amer. Chem. SOC. 1971 93 7106 The Typical Elements 217 C302 gives CCO and CCCO and CNN is formed on trapping carbon atoms in a pure nitrogen matrix.'8b There is continued interest in the lower carbon fluorides and a new static-bomb synthe~is'~" of C,F and a fluorine-plasma synthe~is'~' of (CF) have been described these materials have a high potential for use as lubricants and as cathode materials. Carbonyl fluoride has shown itself to be a good reagent for converting SiOR groups into SiF." The formation of several perfluoro-deriva-tives of azodiformamidine has been described.(NF,),CFN=NCF(NF,) and (NF,),CFN=NC(=NF)NF react with carbon monoxide to give FN=CFN= NCF=NF and FN=CFN=NC(=NF)NF respectively. The reaction of (NF,),CFN=NC(=NF)NF with ammonia followed by fluorination gives (NF,),CN=NCF(NF,) ; the reaction with lithium amide gives the formamidine (NF,),CFN=NC(=NF)NH . lo LiN=C(CF,) substitutes the ketimidegroups for halide in many metal derivatives. Carbonyl derivatives undergo rearrange-ments to give (CF,),C(F)NCO and (CF,),C=NC(CF,),NCO and there are similar rearrangements to -NSO derivatives after reactions with thionyl halides.,lb CF,OOF may be conveniently prepared by fluorinating CF,CO,H in the presence of caesium fluoride,," or from COF and 0,F in the presence of CsF.,,' FC(O)OOC(O)F isomerizes to the ozonide of the unknown difluoro-ketone F2C /O\C = 0 ; strong bases catalyse its diproportionation to \ I 0-0 (CF,OO),CO and CF300C(0)F.22' Very full details of studies on charge-transfer interactions between halides - including CX - and aromatic hydro-carbons and fluorocarbons have now been given.Silicon tetrachloride is an inert non-perturbing medium but most other high-oxidation-state halides show interactions.,, Silicon.-Silicon atoms react with silanes by insertion into Si-H bonds to give silylenes which either polymerize or insert into the Si-H bond of another molecule e.g. CH,SiH gives MeSiH,SiH 1,2-Me2Si,H4 1,3-Me2Si,H,, 1,2,3-Me3Si,H, and Me2Si,H6., Na,Si,, is formed by thermal decomposition of NaSi; between 590 and 720 K 3 < x < 11 ; it has a clathrate lattice with sodium atoms in a polyhedral lattice of silicon.25 l 9 ( a ) R.J. Lagow R. B. Badachhape P. Ficalora J. L. Wood and J . L. Margrave, Synth. Inorg. Metal-org. Chem. 1972,2 145; (6) R. J. Lagow L. R. Shimp D. K. Lam, and R. F. Baddour Inorg. Chem. 1972,11,2568. 2 o R. Muller and D. Mross 2. Chem. 1971 11 382. 2 1 ( a ) J. B. Hynes T. E. Austin and L. A. Bigelow Inorg. Chem. 1972 11 418; (b) R. F. Swindell D . P. Babb T. J. Ouellette and J. M. Shreeve ibid. p. 242. 2 2 (a) D. D. DesMarteau Inorg. Chem. 1972,11 193; ( b ) I. J. Solomon A. J. Kacmarek, W. K. Sumida and J. K. Raney ibid. p. 195; (c) D. Pilipovich C. J. Schack and R. D. Wilson ibid. p. 2531. 23 L. A. Burkhardt P. R. Hammond R. H. Knipe and R.R. Lake J . Chem. SOC. ( A ) , 1971 3789 and following papers. 2 4 P. S. Skell and P. W. Owen J . Amer. Chem. SOC. 1972 94 5434. 2 5 C. Cros and J.-C. Benejat Bull. SOC. chim. France 1972 1739 218 D. W. A . Sharp M. G. H. Wallbridge and J. H. Holloway Silyl bromide reacts with PF,NH to give H3SiNHPF2 ; there are two con-formers present both with PF . . - HN interactions; that present in greatest abundance also has an SiH - FP interaction.26" Various chlorosilylamines, e.g. SiHCl,NHEt have been described as resulting from the reaction between amines and chlorosilanes.26b The formation of silyl-phosphines and -arsines from complex phosphidoaluminates and halogenosilanes has been previously de-scribed,27a and new examples of this reaction to produce Si-PH and Si-PHMe compounds are now Silylphosphine H,SiPH, is best prepared from SiH and PH in the presence of traces of iodine.27C Trisilylamine undergoes a trans-silylation reaction with H2Y (Y = S or Se) to form (H3Si),Y and also salts NH,+(YSiH,)-.The salts react with halides to eliminate ammonium halides, e.g. GeH,Br gives GeH,SSiH which disproportionates to (GeH,),S and (SiH,)2S.28 Phosphorus pentafluoride is a good reagent for converting Si-H into Si-F ;29a halogeno-disilanes and -trisilanes are formed by the action of a silent electric discharge on halogenomonosilanes or by halogenation of trisilanes with BCl or BBr,.29b Direct halogenation of silanes in the absence of solvent is an efficient method of producing bromo-silanes and -germanestgC and iodosilanes.9d Bis(trimethylsily1)mercurials (and the germyl derivatives) react with alkoxides R,MOMe to give unsymmetrical mercurials e.g. Me,SiHgSnMe Several methods are now available for the synthesis of polysilanes. Hexa-alkyldisilanes are formed from chlorosilanes and lithium in hexamethylpho~phoramide,~ I" and sodium-potassium alloy is an effective coupling agent for forming cyclic and cage p~lysilanes.~ I b Halogen can be substituted for methyl in permethylated cyclo-polysilanes by chlorodemethylation with HCl in the presence of AlCl ; some ring contraction also occurs. IC Disilanes undergo symmetrization on heating at 500 K or in the presence of alkoxides e.g. Pr"Me,SiSiMs =(Me,Si) + (Pr"Me,Si) . I d Rearrangements in cyclopolysilanes on irradiation appear to proceed through silylene extrusion ; 1,2,3-trisilacycloheptane derivatives (28) 2 6 ( a ) D .E. J. Arnold E. A. V. Ebsworth H. F. Jessep and D. W. H. Rankin J.C.S. Dalton 1972 1681 ; (6) J. E. Drake and N . P. C. Westwood J . Chem. SOC. ( A ) 1971, 3617. 2' ( a ) D . W. A. Sharp M. G. H. Wallbridge and J. H. Holloway Ann. Reports 1970, 67 A 289; ( 6 ) G. Fritz and H. Schafer Z . anorg. Chem. 1971 385 243; (c) I. H. Sabherwal and A. B. Burg Inorg. Nuclear Chem. Letters 1972 8 27. 2 8 S. Cradock E. A. V. Ebsworth and H. F. Jessep J.C.S. Dalton 1972 359. 29 ( a ) M. A. Finch L. H. Marcus C. Smirnoff C. H. van Dyke and N . Viswanathan, Synth. Inorg. Metal-org. Chem. 1971 1 103; E. W. Kifer and C. H. Van Dyke lnorg. Chem. 1972,11,404; ( 6 ) J. E. Drake and N. P. C. Westwood J .Chem. SOC. ( A ) 1971, 3300; J. E. Drake N . Goddard and N. P. C. Westwood ibid. p. 3305; (c)T. C. Geisler, C. G. Cooper and A. D. Norman Inorg. Chem. 1972 11 1710; (d) F. FehCr B. Mostert A. G. Wronka and G. Betzen Monatsh. 1972,103,959. 30 T. N. Mitchell J . Organometallic Chem. 1972 38 17. 3 1 ( a ) H. Sakurai and A. Okada J . Organometallic Chem. 1972,36 C13; ( 6 ) R. West and A. Indriksons J . Amer. Chem. SOC. 1972,94,6110; E. Hengge and F. Lunzer Synth. Inorg. Metal-org. Chem. 1972 2 93; (c) M. Ishikawa and M. Kumada ibid. 1971 1, 191; (d) H. Sakurai and A. Hosomi J . Organometallic Chem. 1972 36 C15; H. Sakurai and A. Okada ibid. 1972 35 C13 ( e ) H. Sakurai Y. Kobayashi and Y. Nakadaira J . Amer. Chem. SOC. 1971 93 5272; (f) H. Sakurai and M. Murakami, ibid.1972,94 5080; (g) H. L. Carrel1 and J. Donohue Acta Crysr. 1972 B28 1566 The Typical Elements 219 SiMe, SiMe, readily evolve ~ilylenes.~" Insertion of dimethylsilylene into an Si-H bond of a silacyclohexane occurs with retention of c~nfiguration.~'f Me,,Si has the flattened chair configuration of cyclohexane. lg An unstable species trapped from the gas-phase pyrolysis of 1,l-dimethyl-1-silacylobutane has been identified as Me,Si=CH containing a carbon-silicon double bond.32u The sila-alkene is also generated on thermal decomposition of (29).," A great deal of work has been published on the direct synthesis of carbosilanes by conventional condensation reactions e.g. MeSi(CH,SiMe,Br), reacts with lithium and CHBr to give MeSi(CH,SiMe,),CH.33" 1,3,5,7-Tetramethyltetrasila-adamantane Me4Si4(CH2) a product of the pyrolysis of Me4Si has full tetrahedral symmetry.33b The sila-adamantyl radical is readily formed and abstracts halogen from carbon tetra~hloride.~~' Si-C1 bonds in the adamantane are stable to hydrolysis ; LiNEt gives the silylamine which can be recovered from a solution in aqueous hydrochloric acid with the Si-N bond intact.33d Carbon vapour co-deposited with trimethylsilane gives various pro-ducts depending upon the carbon species ; the products include Me4% Me,Si(H.)-CH=CH2 (Me,Si),CH Me,SiCrCH and Me,SiCH=C=CHSiMe which can all be formed following initial insertion into Si-H bonds.34 Si-N bonds are converted into Si-C,F by photochemical reaction with hexafluoro-32 ( a ) T.J. Barton and C. L.McIntosh J.C.S. Chem. Comm. 1972 861 ; (6) T. J. Barton and E. Kline J . Organometallic Chem. 1972 42 C21. 3 3 ( a ) G. Fritz and G. Maass 2. anorg. Chem. 1971,386 163; G. Fritz and M. Hahnke, ibid. 1972 390 104 137 157 185 191; (b) E. W. Krahk R. Mattes K.-F. Tebbe, H. G. von Schnering and G. Fritz ibid. 1972 393 74; (c) G. D. Homer and L. H. Sommer J.C.S. Chem. Comm. 1972 1249; ( d ) C. L. Frye and J. M. Klosowski J. Amer. Chem. SOC. 1972,94 7186. 34 P. S. Skell and P. W. Owen J . Amer. Chem. SOC. 1972,94 1578 220 D. W. A . Sharp M . G. H . Wallbridge and J . H . Hollowuy benzene ;3 pentafluorophenyl-silanes and -germanes are also formed by the reaction between C6F5Br and a silicon%opper catalyst. 5 b N.m.r. spectroscopy has shown that silyl germyl and stannyl derivatives of cyclopentadiene indene, and 2,4-cycloheptadiene undergo rearrangements and exist in all possible isomers, e.g. (30 a - c ) ; 6a bis (t rimet hylgermy1)- and bis( t rime t hy 1stannyl)-cyclopentadien y 1s also undergo rearrangements (c$ p. 226).36b Although Ph3SnC7H7 in the solid has tin a-bonded to a seven-membered ring in the boat conformation with alternating C-C distances the molecule is fluxional in solution.36c Conjugation between two vinyl groups attached to the same silicon seems now to have been unequivocally demonstrated by photoelectron spectro~copy.~~ Crystal structure determinations on Me,M(CN) compounds (M = Si Ge, Sn or Pb) show increasing N . . - M interactions with the heavier elements ; the Si and Ge compounds are approximately tetrahedral molecules with only weak N .- M interaction but in the tin compound planar sheets are formed.38 Pre-parative details for many silazanes have been given the methods generally involving condensation reactions. Amongst the new derivatives are Cl,SiN(p, p’-SiC1,),NSiCl3 ;39a ring systems containing N-N links e.g. (31)39b [a ten-3 5 ( a ) J. M. Birchall R. N. Haszeldine M. J. Newlands P. H. Rolfe D. L. Scott A. E. Tipping and D. Ward J. Chem. SOC. ( A ) 1971 3760; ( b ) M. Weidenbruch and N. Wessal Chem. Ber. 1972 105 173. E. W. Abel and M. 0. Dunster J. Organometallic Chem. 197 1,33,161; G. I. Avramenko, N. M. Sergeyev and Y . A. Ustynyuk ibid. 1972,37,89; P. E. Rakita and G. A. Taylor, Inorg. Chem. 1972 11 2136; A. V. Kisin V. A. Korenevsky N. M. Sergeyev and Y.A. Ustynyuk J. Organometallic Chem. 1972 34 93; S. R. Stobart ibid. 1972 43, C26; M. D. Curtis and R. Fink ibid. 1972 38 299; C. H. Campbell and M. L. H. Green J. Chem. SOC. ( A ) 1971 3283; ( b ) Y. A. Ustynyuk A. V. Kisin and A. A. Zenkin J. Organometallic Chem. 1972,37,101; ( c ) J. E. Weidenborner R. B. Larrabee, and A. L. Bednowitz J. Amer. Chem. SOC. 1972,94,4140. U. Weidner and A. Schweig J. Organometallic Chem. 1972 37 C29; Angew. Chem. Internat. Edn. 1972 11 536. 3’ 3 8 J. Konnert D. Britton and Y. M. Chow Acta Cryst. 1972 B28 180. 3 9 ( a ) U. Wannagat H. Moretto and P. Schmidt Z. anorg. Chem. 1971 385 164; ( b ) U. Wannagat E. Bogusch and F. Rabet ibid. p. 261 ; U. Wannagat and S. Meier, ibid. 1972 392 179; U. Wannagat L. Gerschler and H.-J.Wismar Monatsh. 1971, 102 1834; (c) U. Wannagat and E. Bogusch ibid. p. 1806; U. Wannagat E. Bogusch, and P. Geymayer ibid. p. 1825; L. W. Breed and J. C. Wiley jun. Inorg. Chem., 1972 11 1634; ( d ) U. Wannagat E. Bogusch P. Geymayer and F. Rabet Monatsh., 1971 102 1844; 1. Haiduc and H. Gilman Synth. Inorg. Metal-org. Chem. 1971 1, 69 75; ( e ) D. Mootz J. Fayos and A. Zinnius Angew. Chem. Internat. Edn. 1972 11, 58 The Typical Elements Me2 Si MeN' \ I NMe 22 1 membered Si,N system rearranged to the Si,N4 cyclotetrasilazane system with two exocyclic amino-groups and ammonolysis of 1,3-dichlorotetramethyl-disilazanegave both Si,N and Si,N systems]. Derivatives withother than simple alkyl substituents are obtained by condensation or by subsequent reaction e.g.[Me,Si=NH] reacts with HX to give XSiMe2N(pp'SiMe,),NSiMe,X.39' Con-densation reactions with urea derivatives siloxanes or silanediols give ring sys-tems incorporating C and 0.39d It seems probable that the structures of some of these silazanes are more complex than has been assumed previously. The reaction of SiC1 and NaN(SiMed2 gives (32) which has a two-ring spiran SiMe SiMe, I I N N / \ . / \ Me,Si S1 SiMe, \ / \ / CH N I I SiMe SiMe, Enaminosilanes R,C=NSiMe,Cl,- (R = Bu'or Ph) are formed from R,C=NLi and the chlorosilane. The t-butyl derivatives appear to have linear CNSi skeletons whereas the phenyl derivatives may have a bent arrangement.,'" The olefins ( CF,)2C=C(CN)2 and CF,( CF,Cl)C=C( CN) undergo 174-addi tion with Si, Ge and Sn derivatives e.g.Me,SiSMe gives (CF,),C(SMe)C(CN)=C=N-SiMe ,40b N,O-bis(organosily1)-hydroxylamines RMe,SiNHOSiMe,R rearrange to the N,N-derivatives in the presence of base,41a whilst tris(organosily1)-hydroxylamines (R,Si),NOSiR rearrange on heating to silylaminosiloxanes R,SiN(R).SiR,-OSiR ,,lb and (33a) is in tautomeric equilibrium with (33b).,l' NN-Bis(organosily1)-hydroxylamines can be oxidized to nitroxide radicals by oxygen.41a Silyl azides e.g. Me,Si(N,) are readily formed from chlorosilanes ( a ) J . B. Farmer R. Snaith and K. Wade J.C.S. Dalton 1972 1501; E. W. Abel, J. P. Crow and J . N. Wingfield ibid. p. 787. ( a ) R. West and P. Boudjouk J . Amer. Chem. SOC. 1971 93 5901 ; ( 6 ) P. Boudjouk and R. West ibid. p. 5901 ; ( c ) B. Dejak and Z .Lasocki J . Organometallic Chem. 1972, 44. c 3 9 . 222 D. W. A . Sharp, CH,CON M. G. H. Wallbridge and J . H. Holloway and sodium azide in (Me,N),PO or HCONMe ;42a on photolysis trialkylsilyl azides give cycl~disilazanes.~~~ The product from the reaction between Me,SiN, and Fe,(C0)9 contains a Me,SiN group symmetrically bonded to three iron Silyltriazenes e.g. ArNNN(SiX,) are formed in reactions between triazenides and halogenosilanes or diazonium salts and bis(sily1)amides ; the silyl groups undergo migration throughout the nitrogen chain ;43a the tetrazene (Me,Si),N-N=N*N(H)SiMe is formed by hydrolysis of Me,SiN=NSiMe ; it decomposes thermally to an azide and a bi~(sily1)arnine.~~’ Although hexa-chlorodisilane undergoes disproportionation in the presence of amines in the presence of diphosphines and diarsines derivatives such as Me,AsSiCl are formed.44 Silicon monoxide behaves as a very reactive silylene and when condensed with organic compounds at low temperatures inserts into various bonds to give The methods of synthesis of a-difunctional oligosiloxanes have been critically and cyclocarbosiloxanes have been re~iewed.~” Silyl groups particularly the Me,Bu‘Si group appear to have great potential for the protection of hydroxy-groups ;46a silicones are formed during the thermal decomposition of bis(silyl)peroxides e.g.Ph,SiOOSiPh gives Ph,SiOSi(OPh)-Ph .46b Monomeric imino-oxysilanes e.g. Me,Si(ON CMe,) are readily formed by elimination reactions between chlorosilanes and ~ximes.~’ Bis-(trifluoromethyl)thioketen (CF,),C=C=S undergoes addition reactions with silanes and stannanes to form for example Et,SiSCH=C(CF,) .48 Studies of coupling constants in methylchlorosilyl radicals in solid matrices show that the structures of the radicals deviate more and more from planarity with the degree of substitution of methyl by chlorine.49 Studies on MeMX derivatives (M = Si, 4 2 ( a ) S .S . Washburne and W. R. Petersen jun. J . Organometallic Chem. 1971 33, 153 ; ( 6 ) D. W. Klein and J. W. Connolly ibid. p. 3 1 1 ; (c) B. L. Barnett and C. Kruger, Angew. Chem. Internat. Edn. 1971,10,910. ‘’ (a) N. Wiberg and H. J. Pracht Chem. Ber. 1972,105 1377 1388; ( b ) N . Wiberg and W. Uhlenbrock ibid. p. 63. 44 T. A. Banford and A. G. MacDiarmid Inorg. Nuclear Chem. Letters 1972,8 733.4 5 (a) E. T. Schaschel D . N . Grey and P. L. Tirnrns J. Organometallic Chem. 1972,35, 69; ( b ) M. G. Voronkov and N. G . Sviridova Russ. Chem. Rev. 1971 40 819; ( c ) N. S. Nametkin T. K. Islarnov L. E. Gusel’nikov and V. M. Vdovin ibid. 1972,41, 111. 46 ( a ) E. J . Corey and A. Venkateswarlu J. Amer. Chem. SOC. 1972 94 6190; ( b ) A. K. Shubber and R. L. Dannley J . Org. Chem. 1971,36 3784. 4 7 A. Singh A. K. Rai and R. C. Mehrotra J.C.S. Dalton 1972 191 1. 4 8 M. S. Raasch J. Org. Chem. 1972,37 1347. 4 9 C. Hesse N. Leray and J. Roncin J . Chem. Phys. 1972 57 749 The Typical Elements 223 Ge or Sn)give bond-energy termsE(C-X) -= E(Si-X) > E(Ge-X) > E(Sn-X) generally although E(C-Y) > E(Si-Y) for Y = H or Me. The softness (mea-sured in terms of AH) of the series Me,Mf increases in the order C < Si < Ge < Sn.” Although perfluoroalkylfluorosilanes have been mentioned previously, R,SiF are best prepared by fluorination of the R,SiF,I compounds which result from the reaction between R,I and SiF ;’ they decompose thermally by elision of fluorocarbenes.Tri-imidodisiloxane Si,O(NH) is formed by ammonolysis of Cl,SiOSiCl, at low temperatures; it decomposes thermally to the oxynitride Si,0N,.52 A large number of silatranes e.g. EtOSi(OCH,CH,),N with oxy substituents at the apical silicon atom have been described; the strength of the transannular N-Si bond is increased by the presence of an electron-withdrawing apical substituent. 53 Biguanide and guanylurea form stable cationic species with silicon.54 Silicon tetrafluoride undergoes ammonolysis or hydrolysis with amines or hydroxy-compounds ; fluorosilazanes or silicates can be isolated from the reaction mixtures but fluorosilicates are also formed. ’ ’ The dark green solid of stoicheiometry Cl,Si(bipy) formed by the action of Li,(bipy) on SiCl,,bipy appears to consist of two isomers (i) a hexaco-ordinate silicon compound Cl,Si(bipy) in both singlet and triplet states and (ii) a tetraco-ordinate silicon compound [Cl,Si(bipy)] [bipy]. In all cases the bipyridyl is present as radical anion^.'^" Complexes (py),SiCl,X and (py),SiCl,X and the corresponding o-phenanthroline derivatives have been prepared ; the structures are such that the larger halogen is out of the plane occupied by bulky ligands ; SiC1 groups are generally T shaped.56b One form of SiO, stishovite has the rutile structure and in this as in most other oxides with this structure two of the Si-0 distances are slightly longer than the other four (in CrO, RuO, and OsO this pattern is not f~llowed).’~ Zeolites with framework structures have large holes in which H,O NH, S8 rings in a crown configuration and acetylene can be present.’” The structures of crystals containing these sorbed molecules show them to be held by induced dipole forces.The rare-earth silicates M,0,,2Si02 contain chain Si,O Silicon catecholates and related derivatives e.g. (C,H,O,),Si and monomeric and dimeric C,H,O,SiCl, are formed from the diol and SiCl, J. C. Baldwin M. F. Lappert J. B. Pedley and J. S. Poland J.C.S. Dalton 1972 1943.K. G. Sharp and T. D. Coyle Inorg. Chem. 1972,11 1259. 5 2 P. Goursat D. Giraud and M. Billy Bull. SOC. chim. France 1972 3681. s3 C. L. Frye G. A. Vincent and W. A. Finzel J . Amer. Chem. SOC. 1971,93,6805. s 4 A. Maitra and D. Sen Inorg. Nuclear Chem. Letters 1972 8 793. s 5 d. J. Harris and B. Rudner J . Inorg. Nuclear Chem. 1972 34 75. 5 6 (a) P. M. Broudy A. D. Berry B. B. Wayland and A. G. MacDiarmid J . Amer. Chem. Soc. 1972,94 7577; (b) D. H. Boa1 and G. A. Ozin Cunad. J. Chem. 1972,50,2484. 5 7 W. H. Baur and A. A. Khan Actu Cryst. 1971 B27 2133. s8 ( a ) P. E. Riley K. Seff and D. P. Shoemaker J. Phys. Chem. 1972 76 2593; R. Y. Yanagida and K. Seff ibid. p. 2597; K . Seff ibid. p. 2601 ; A. A. Amaro and K. Seff, J.C.S. Chem. Comm. 1972 1201; (b) J.Felsche Naturwiss. 1972 59 3 5 . ” ( a ) H. R. Allcock T. A. Nugent and L. A. Smeltz Synth. Inorg. Metal-org. Chem. 1972, 2 97; (b) D . W. Barnum Inorg. Chem. 1972 11 1424; ( c ) G. Schott and D. Lange, Z . anorg. Chem. 1972,391,27 224 D. W. A . Sharp M. G. H . Wallbridge and J. H. Holloway triscatecholates often crystallize with an extra molecule of solvent and this is so firmly bound that it is probably co-ordinated to Oxalato derivatives, e.g. (R4N),Si(C204), (R,N),Ph,M(C,O,) (M = Si or Ge) are formed from chlorosilanes and silver oxalate and are very stable to hydrolysis ; compounds (R,N)RSi(C,O,) are very unstable to hydrolysis. 59c Alcoholysis of SiS gives (Bu'O),Si(SH) .60 Cd,SiS, like many other sulphides has SiS and CdS, tetrahedra linked by sharing corners ; the packing of sulphur atoms is strongly Na,Si,S, has adamantane-like Si,SIo4-Pt(Ph,P) reacts with silicon tetrafluoride to give (Ph,P),Pt.SiF which is suggested to contain a Pt-Si bond with five-co-ordinate silicon.62 What is probably an electronically excited form of SiF is produced when silicon tetra-fluoride is passed over silicon or silicon carbide at 1500-2230 K.With BF it gives SiF,BF in addition to known silicon boron fluoride^.^^" Co-condensation of SiF with B,H6 gives various silanes including H,SiSiF H,Si(SiF,),, HSi(SiF,) and Si(SiF,),. No silicon-boron compounds are isolated but the reducing conditions clearly lead to interesting SiF reacts with unsaturated compounds with formation of heterocyclic derivatives and insertion into bonds.Substrates that give reactions with SiF include fluoroalkenes buta-diene allene and acetylenes.63c Pyrolysis of chloro-silanes in the presence of acetylene gives products which whilst not precisely similar to those from reactions of SiF, suggest strongly that SiCI has been formed as an intermediate.63d From their e.s.r. spectra the radicals SiH,F SiHF, SiF, and Me,SiF all have pyramidal geometry about the silicon atom.64 Perchloropolysilanes form crystalline adducts with SiC1 ; in Si,Cl,,,SiCI the molecules of the two chloro-silanes are merely stacked together in the crystal.65 Finally the halogenosilane FClBrISi has been prepared by the procedure : h SiFBr SbC'3 b SiFClBr HS113 h SiFBrClI.66 SbF SiBr, Germanium.-GeX radicals are pyramidal and GeX species are bent when isolatedininert matrices.67 Thethreegermylpseudohalides,H,GeN ,H,GeNCO, and H,GeNCNGeH all have non-linear skeletons in the gas phase as is found h o W.Wojnowski and M. Wojnowska Z. anorg. Chem. 1972 389 302. 6 1 ( a ) B. Krebs and J. Mandt 2. anorg. Chem. 1972 388 193; A Cade M. Ribes E. Philippot and M. Maurin Compt. rend. 1972,214 C 1054. " T. R. Durkin and E. P. Schram Inorg. Chem. 1972 11 1042. 6 3 ( a ) D. L. Smith R. Kirk and P. L. Timms J.C.S. Chem. Comm. 1972 293; (b) D. Solan and A. B. Burg Inorg. Chem. 1972 11 1253; ( c ) A. Orlando C . S. Liu. and J . C. Thompson J. Fluorine Chem. 1972/3,2 103; J . C. Thompson and J. L. Margrave, Inorg. Chem. 1972,11,913; Y.-N. Tang G. P. Gennaro and Y. Y. Su J. Amer. Chem. SOC. 1972 94 4355; C. S. Liu and J .C. Thompson J. Organometallic Chem. 1972, 38,249; C. S. Liu J . L. Margrave J. C. Thompson and P. L. Timms Canad. J. Chem., 1972 50 459; C. S. Liu J. L. Margrave and J. C. Thompson ibid. p. 465; (d) E. A. Chernyshev N. G. Komalenkova and S. A. Bashkirova J. Gen. Chem. ( U . S . S . R . ) , 1971,41 1177. 6 4 M. V. Merritt and R. W. Fessenden J. Chem. Phys. 1972 56 2353. 6 5 D. K. Fleming Acta Cryst. 1972 B28 1233. 6 6 F. Hofler and W. Veigl Angew. Chem. internat. Edn. 1971 10 919. 6 7 G. R. Smith and W. A. Guillory J. Chem. Phys. 1972,56 1423; R. J . Isabel and W. A. Guillory ibid. 1972 57 1 1 16 The Typical Elements 225 for methyl analogues rather than for silyl species (cf p. 21 5).68" Halogenogermanes and lithium hydrazides give germylhydrazines including cyclic derivatives ; for derivatives of the type Me,NN(R)GeR the metalloid-nitrogen is basic and undergoes attack.68b Many germylarsines e.g.GeH ,AsMe and Me,Ge(AsMe,) , have been prepared by the reaction of aluminium and lithium arsenides or silyl-arsines with germanium halides.69 Specific methods for the preparation of monohalogenogermanes involve the use of thionyl chloride or boron tribromide with GeH4.70 Co-condensation of germanium or tin atoms with carbon monoxide into matrices at 20 K gives carbonyls probably GeCO and SnCO the first reported carbonyls for these element^.^ Generally a phenyl derivative of a non-metal hydride is more acidic than the parent hydride but the phenylgermanes constitute an exception to this rule. A possible explanation for the phenomenon lies in the lack of p-character in the germanium lone pair of for example the PhGeH,- ion and the consequent lack of pn-pn interaction between the phenyl group and the germanium.Permethylcyclopolygermanes can be prepared by coupling reactions using lithium or organometallic derivatives on halogenogermanes ; the polygermanes undergo redistribution reactions as do polysilanes. 73a Phenyl-halogenogermylenes insert into Ge-X bonds of phenylhalogenogermanes to give polygermane~.~~' Ge-X bonds add readily across double bonds to produce saturated derivatives. Examples described include addition to N=N N=O, and C=C.74a Addition of Me,MNMeM'Me (M,M' = Si Ge or Sn) to iso-cyanates or isothiocyanates gives varying products depending upon the affinity of M for 0 N or S and the tendency for the Me,M group to migrate.Tendencies for bond formation are Me3Si 0 > S 2 N Me,Ge S > 0 2 N; Me,Sn : S > 0 > N.74b Ph,GeOOH reacts with Et,Tl to give Ph,Ge00T1Et2; on heating the peroxide yields Et,TiOGePh,OPh and a similar derivative is formed if a silyl peroxide is used.75" 'Germyl sulphinates R ,Ge02SR2 are formed from the bromogermane and the appropriate silver Mass spectral studies on methylchlorogermanes suggest that there is a large decrease in the Ge-C1 bond strength with increase in the number of chlorine atoms present.76 " ( a ) J . D . Murdoch and D . W. H. Rankin J.C.S. Chem. Comm. 1972,748; L. K. Peter-son and K. I . The Canad. J . Chem. 1972,50 5 5 3 562. b9 J . W. Anderson and J . E. Drake J.C.S. Dalton 1972 951.7 0 J . W. Anderson and J. E. Drake Synth. Inorg. Metal-org. Chem. 1971 1 155; J. W. Anderson G . K. Barker J. E. Drake and R. T. Hemmings Canad. J . Chem. 1972, 50 1607. A. Bos J.C.S. Chem. Comm. 1972,26. 72 W. L. Jolly Inorg. Chem. 1971 10 2364. 7 3 ( a ) E. Carberry B. D. Dombeck and S. C. Cohen J . Organometallic Chem. 1972 36, 61 ; E. J . Bulten and J. G. Noltes Rec. Trav. chim. 1972 91 1041 ; ( 6 ) P. Riviere and J. Satge Synth. Znorg. Metal-org. Chem. 1971 1 13. 7 4 ( a ) K.-H. Linke H. J. Gohausen and G. Wrobel Chem. Ber. 1972,105 1780; J. Satge, M . Lesbre P. Riviere and S. Richelme J . Organometallic Chem. 1972 34 C18; J. Satge C. Couret and J . Escudie ibid. p. 83; ( b ) K. Itoh T. Katsuura I. Matsuda, and Y . Ishii ibid. p. 63. 7 5 ( a ) G.A. Razuvaev V. A. Dodonov T. I. Starostina and T. A. Ivanova J. Organo-metallic Chem. 1972 37 233; ( b ) E. Lindner and K. Schardt ibid. 1972,44 1 1 1 . 76 J. Tamas G. Czira A. K. Maltsev and 0. M. Nefedov J . Organometallic Chem., 1972,40 311 226 D. W. A . Sharp M. G. H. Wallbridge and J. H. Holloway Dichloro(phthalocyanino)germanium(Iv) is reduced by sodium borohydride to phthalocyaninogermanium(~~). GeCl,,NMe has trigonal-bipyramidal co-ordination about the germanium with nitrogen occupying an axial position.78 Clathrate-type compounds Ge,,M& (M = P As or Sb) are formed by heating the elements ; iodineatoms are present in cavities formed by the Ge-M skeleton.79 GeSb is formed in the Ge-Sb system ; it has a new structure type with an atomic configuration intermediate between those of Sb and Ge.80 but in the pH region 2-6 only mononuclear species Ge(OH),(4-")+ are present.81 Gd,Ge,O contains chain Ge,O and GeO groups.82u Magnesium germanate has the unit-cell composition Mg,8Ge,o0,8 .82b When magnesium fluoride is added and the material is grown from a PbF flux (a process which gives an efficient phosphor) structurally related Mg&e7.,O,,F,O is obtained.82c K,Ge(IO,) has a regular octahedral arrangement of oxygen about each ger-manium; each iodine group is in a very distorted octahedral c~nfiguration.~~ Thiolates [R,1N][R,2M(mnt)] [M = Ge Sn or Pb; R2 = Me or Ph; mnt = dicyanoethylene- 1,2-dithiolate] are formed from the halogenometallates and sodium thiolates ; with RMX derivatives bond cleavage occurs.84 Tin.-?-Irradiation of tin or lead salts gives Sn3+ and Pb3+ ions.85 In the vapour phase electron diffraction indicates only one form with gem-SnMe, groups for C,H,(SnMe,) (cf p.220).86 Hydride abstraction from positions B to carbon-metal bonds including tin is extremely facile and thus Ph,CBF, reacts with Me,SnEt with attack on the ethyl group to give Me,SnBF and ethylene.87 Dicyclopentadienyltin(I1) readily undergoes protolysis to tin(@ derivatives and many compounds that were previously inaccessible e.g. Sn(OMe) , Sn(OSiPh,) and Sn(SPh) may be prepared by this route.88 Co-ordination compounds between ethylenediamine and diaryltin dihalides are formed by direct interaction of the components spectroscopic studies Germanium(1v) at pH 0 to 2 exists as species Ge[Ge(OH)],'4+3")+ (n = 1-10), " R.L. Stover C. L. Thrall and R. D. Joyner Inorg. Chem. 1971,10,2335. " 7 9 H.-G. von Schnering and H. Menke Angew. Chem. Internat. Edn. 1972 11 43; H. M. S. Bilton and M. Webster J.C.S. Dalton 1972 722. Menke and H.-G. von Schnering Naturwiss. 1972,59 420. B. C. Giessen and C. Borromee-Gautier J . Solid State Chem. 1972 4 447. I. I . Alekseeva and I. I. Nemzer Russ. J. Inorg. Chem. 1971 16 987. ( a ) Y. I. Smolin Y. F. Shepelev and I . K. Butikova Sovier Phys. Cryst. 1972 16, 790; (b) D. W. A. Sharp M. G. H. Wallbridge and J. H. HLlloway Ann. Reports, 1971 68 B 309; ( c ) P. W. Bless R. B. von Dreele E. Kosher and R. E. Hughes, J . Solid Stute Chem. 1972,4 262. 8 3 F. Schellhaas H. Hartl and R. Frydrych Acra Cryst. 1972 B28 2834.8 4 E. S. Bretschneider and C. A. Allen. J . Organometallic Chem. 1972,38,43. 8 5 R. J. Booth H. C. Starkie and M. C. R. Symons J . Phys. Chem. 1972 76 141. 8 6 N. N. Veniaminov Y. A. Ustynyuk N. V. Alekseev I. A. Ronova and Yu. T. Struch-kov J. Struct. Chem. 1971 12 879. 8 7 J . M. Jerkunica and T. G. Traylor J. Amer. Chem. SOC. 1971,93 6278. P. G. Harrison J.C.S. Chem. Comm. 1972 544. 89 ( a ) T. N. Srivastava and K. L. Saxena J . Inurg. Nuclear Chem. 1971 33 3996; (6) J. C. May and C. Curran J . Organometallic Chem. 1972 39 289; ( c ) G.-E. Matsu-bayashi M. Hiroshima and T. Tanaka J. Inorg. Nuclear Chem. 1971,33 3787 The Typical Elements 227 suggest that terpyridyl complexes of R,Sn(NCS) have seven-co-ordination about tin with axial C-Sn-C bonds.*” Picolinamide and related ligands bond to the tin of Me,SnCl through the ring nitrogen and carbonyl oxygen (the ligand is either chelating or bridging); the thioamides only bond through the ring nitrogen.89c Aminophenols and related compounds react with dialkyltin oxides to give species of the type R2Sn(o-H2NC6H40)(OH) with chelated amino-phenolate ;’& a stannatrane PhSn(OCH,CH,),N is formed from [PhSn(O)OH], and triethanolamine ; there appears to be an N -+ Sn bond.’Ob [NN’-ethylenebis-(salicylideneiminato)]dimethyltin(~v) has a trans-octahedral co-ordination about tin with co-ordination from oxygen and nitrogen of the Schiff’s base;’” com-plexes of uncharged Schiff’s bases R,SnCl ligand are suggested to have weak co-ordination from nitrogen.’ I b There is considerable interest in organotin azoles.Tin triazoles and tetrazoles are formed by cycloaddition of a tin azide to alkynes or nitriles or by condensation of triazoles or tetrazoles with tin oxides or hydroxides triorganotin azoles are considered to have bridging azole groups and five-co-ordinate tin.’,’ Tributylstannyldiphenylmethyleneamine, Bu,SnN=CPh reacts with multiple bonds in cyanates ketones nitriles, sulphur oxides etc. to give stannyl derivatives e.g. Bu,SnOC(S)N=CPh from OCS.93” Stannyliminosulphuranes e.g. Me S(NSnMe,) are formed from the di-imide and chlorostannanes or by transamidation ; the tin iminosulphuranes undergo insertion reactions with CO for example.’,’ Organotin pseudohalides continue to be widely studied. Nitrosodicyanomethanides e.g.Ph,SnONC(CN) , are prepared from the corresponding silver salts.’& Stannyl carbodi-imides, e.g. Ph,SnNCNSnPh, give tin sulphides with thioureas and react with cyan-amide to give the cyanamide Ph,SnNHCN,94b Thiocyanogen cleaves an Sn-C bond of tetraorganotin derivatives Me,SnR (R = 2-butenyl 2-propynyl etc.) to form tin is~thiocyanates.’~‘ Metathetical exchange between tin alkoxides and aminosilanes gives sulphinylaminotin derivatives e.g. BU,S~NSO.’~ Exchange and hydrolysis of R,SnCl with sodium azide in water gives azidostannoxanes, e.g. (34).94e Me,SnCl and AgOCN give an isocyanate hydroxide Me,SnNCO, Me,SnOH ; Me,Sn groups are bridged by alternating nitrogen (from NCO) and oxygen (from OH) and there is extensive hydr~gen-bonding.’~f The stannyl-90 ( a ) R.C. Mehrotra and B. P. Bachlas J . Organometallic Chem. 1972 40 129; (6) A. G. Davies L. Smith and P. J. Smith ibid. 1972,39 279. 9 1 ( a ) M. Calligaris G. Nardin and L. Randaccio J.C.S. Dalton 1972 2003; (b) K. Kawakami M. Miya-Uchi and T. Tanaka J . Inorg. Nuclear Chem. 1971,33,3773. 92 ( a ) S. Kozima T. Itano N . Mihara K. Sisido and T. Isida J . Organometallic Chem., 1972 44 117; K. Sisido K. Nabika T. Isida and S. Kozima ibid. 1971 33 337; (b) R. Gassend M. Delmas J.-C. Maire Y. Richard and C. More ibid. 1972 42, C29. 93 (a) P. G. Harrison J.C.S. Perkin I 1972 130; (b) D. Hanssgen and R. Appel Chem. Ber. 1972 105 3271. 94 ( a ) H. Kohler U. Lange and B. Eichler J . Organometallic Chem. 1972 35 C17; (6) R. A. Cardona and E. J . Kupchik ibid. 1972,34 129; 1972,43 163; (c) M.L. Bullpitt and W. Kitching ibid. 1972 34 321 ; (4 D. A. Armitage and A. W. Sinden. ibid., 1972 44 C43; (e) H. Matsuda F. Mori A. Kashiwa S. Matsuda N. Kasai and K. Jitsumori ibid. 1972 34 341; (f) J. S. Thayer and D. P. Strommen ibid. 1966, 5 383; J. B. Hall and D. Britton Acra Crysr. 1972 B28 2133 228 D. W. A . Sharp M . G. H . Wallbridge and J . H . Holloway Bu 0 0 OH \ / \ / \ / Sn S Sn / \ / \ / \ HO 0 0 Bu (34) (35) phosphide Me,SnPHPh undergoes controlled oxidation to Me,SnOPHPh ; further oxidation appears to give a ph~sphonate.~~ Trialkyltin alkoxides can be prepared by thermal decomposition of a mixture of the oxide and the dialkyl carbonate or except for Me,SnOR and Et,SnOR, by distillation of the oxide and an alcohol.96 The compound [CpFe(CO),-SnPh(OSOPh)(OH)] contains two five-co-ordinate tin atoms linked by two hydroxyl bridge^.^'" The species [(EtSn) o(OH)28]2 + which is present in basic aqueous solutions of ethylstannyl derivatives depolymerizes to [(Etsn),(OH),,] +, [(EtSn),(OH),,] and [(EtSn),(OH),,]- on increasing the pH; in 1M-NaOH, EtSn(OH) and [EtSn(OH),]- are present.97b Insoluble polymeric peroxides are formed when R,Sn(OMe) are treated with hydrogen per~xide.~' The adduct formed bet ween triphenylphosphineacetylmethylene and SnCl has an 0 -+ Sn bond rather than a C-Sn bond as is found in the corresponding methylene~.~~ From Mossbauer spectroscopy it is concluded that Me,SnNO has planar Me3Sn groups with bridging nitrates Me,Sn(NO,)H,O has a planar Me3Sn group with co-ordinated unidentate nitrate and water.' Oob A similar geometry is found in the hydroxamate Ph,SnONPhCOPh the carbonyl oxygen being intramolecularly co-ordinated.l o l a Stannyl oximes e.g. Me,SnONHCOPh, are readily formed from hydroxylamines and the tin oxide or hydroxide ;' ' I b benzil oximes give adducts with tin tetrahalides."'" Insertion reactions of SO, into Sn-C bonds continue to receive wide study. In related studies it has been shown that oxidation of alkyldithiostannonic acids with hydrogen peroxide gives orthosulphites e.g. (35).'02 1 1 and 1 2 addition compounds of R,SnCl, (R = Me or Ph) with R,EO (E = C N P or S) all have 0 -+ Sn bonding. The 9 5 P. G. Harrison S. E. Ulrich and J. J. Zuckerman Inorg. Chem. 1972 11 25. 9 6 (a) A. G. Davies D.C. Kleinschmidt P. R. Palan and S. C. Vasishtha J. Chem. Soc. (0 1971 3972. 9 7 (a) R. Restno and R. F. Bryan J. Chem. Soc. ( A ) 1971,3364; ( 6 ) M. Devaud J. Chim. phys. 1972 69 460. 98 R. L. Dannley W. A. Ave and A. K. Shubber J. Organomerallic Chem. 1972 38, 281. 9') J. Buckle P. G. Harrison T. J . King and J. A. Richards J.C.S. Chem. Comm. 1972, 1104. l o o (a) R. C. Poller and J. N. R. Ruddick J. Organomerallic Chem. 1972 39 121; (b) R. E. Drew and F. W. B. Einstein Acta Cryst. 1972 B28 345. Io1 (a) T. J. King and P. G. Harrison J.C.S. Chem. Comm. 1972 815; (6) P. G. Harrison, J. Organomelallic Chem. 1972 38 C 5 ; (c) K. M. Ah J. Charalambous and M. J. Frazer J.C.S. Dalton 1972 207. l o * C. H. Stapfer and R. H. Herber J. Organomerallic Chem. 1972 35 11 1 The Typical Elements 229 bis complexes generally have cis-C1 and cis-donor arrangements; the 1 1 complexes generally have trigonal-bipyramidal geometry about tin with the donor and one C1 in the apical position^."^ (MeSn),S has the expected adamantane-like structure.O4 Dicyclopentadienyltin(I1) and SnX (X = C1 or Br) interact to give a new series of tin(r1) compounds CpSnX which probably contain halogen bridges.lo5 One of the products from the reaction between CpMo(CO),Cl and (Me,Sn),S is [Cp3M03S4]+ [Me,SnCl,]- having a trigonal-bipyramidal anion with a planar Me,Sn group.'06 Solvolysis of methyltin chlorides in anhydrous HF gives for example MeSnF and mixed chloride fluorides. lo' Sn[(OC2H,)2NC2H,0H]2 prepared from SnC1 and triethanolamine has octahedrally co-ordinated tin;'" tin(1v) ethylenediaminetetra-acetate mono-hydrate has seven-co-ordinate tin co-ordination being from two nitrogens four carboxylate oxygens and the water.Ethyleneurea is considered to co-ordinate to SnX (X = C1 Br or I) through the oxygen; ethylenethiourea co-ordinates through the imino-nitrogen. l o The phase Sno.,P is now recognized as SnP,; the structure contains layers of puckered P6 rings connected by Sn atoms and is related to one of the forms of arsenic;"' the phase GeP is iso-structural. The distorted co-ordination expected about tin(I1) is clearly shown in the structures of SnSO (pyramidal co-ordination by oxygen),' I 2a P-SnW04 (three short plus three long bonds),' 12' and the hydrates 2SnBr,,H,0"2' and 6SnBr2,-5H20' l Z d (trigonal prismatic with extra atoms in faces).Addition of dioxan to an alcoholic solution of SnCl gives crystals of (SnC1,0H,H20),,3dioxan. Each tin(rv) atom has octahedral co-ordination and tin atoms are linked by bridging hydroxy-groups to form dimers ; the dioxan molecules are unco-ordinated. ' l 3 Many tin(rv) complexes of oxygen-containing ligands have been described but only characterized structurally by spectroscopic means. Tin@) is extracted from SnC1,-HCI solutions generally as SnCl, 2H20 and H2SnC16 although solutions in tributyl phosphate (TBP) contain cis-SnC14,2TBP. SnCl in disulphuric acid gives H,[Sn(HSO,),].' Addition of base to the previously B. V. Liengme R. S. Randall and J . R. Sams Canad. J . Chem. 1972,50 3212. D . Kobelt E. F. Paulus and H.Scherer Acta Cryst. 1972 B28 2323. P. J. Vergamini H. Vahrenkamp and L. F. Dahl J . Amer. Chem. SOC. 1971,93,6327. H . Follner Monarsh. 1972 103 1438. l o ' K. D. Bos E. J. Bulten and J. G. Noltes J . Organometallic Chem. 1972 39 C52. l o ' L. E. Levchuk J. R. Sams and F. Aubke Inorg. Chem. 1972 11 43. ' O M l o ' F. P. van Remoortere J . J . Flynn and F. P. Boer Inorg. Chem. 1971 10 2313. ' l o P. P. Singh and 1. M. Pande J . Inorg. Nuclear Chem. 1972,34 591. ' I 1 J. Gullman and 0. Olofsson J . Solid State Chem. 1972 5 441. 'I2 (a) J. D . Donaldson and D . C. Puxley Acta Cryst 1972 B28 864; ( b ) W. Jeitschko and A. W. Sleight ibid. p. 3174; (c) J . Anderson Acta Chem. Scand. 1972 26 1730; (4 J. Anderson ibid. p. 2543. N. G. Bokii and Yu. T. Struchkov J .Struct. Chem. 1971 12 253. (a) M. J . Taylor J. R. Milligan and D. L. Parnell J . Inorg. Nuclear Chem. 1972 34, 2133; ( 6 ) R. C. Paul J . K. Puri V. P. Kapila and K. C. Malhotra ibid. p. 2141; ( c ) D . W. Thompson J . F. Lefelhocz and K. S. Wong Inorg. Chem. 1972 11 1139; (d) R. C. Paul V. Nagpal and S. L. Chadha Inorg. Chim. Acla 1972 6 335; ( e ) P. G. Harrison B. C. Lane and J. J. Zuckerman Inorg. Chem. 1972 11 1537 230 D. W. A . Sharp M. G. H. Wallbridge and J. H . Holloway described adducts Cl,Sn(acacH) gives the anionic species [SnCl,(acac)] -. 14c Alkoxytin(1v) trihalides give 1 1 adducts with ligands containing P-0 and N-0 bonds;114d the tetrahalides give 1 2 adducts with similar oxygen-contain-ing and also phosphine and arsine ligands and cis- and trans- isomers of these adducts have been identified.4e The phases present in the Na,S + SnS system are Na,SnS, Na,Sn,S,, Na,SnS and Na,Sn,S ."" The Sn2S76- ion in Ba,Sn,S7 contains linked tetrahedra. l 1 '' PbSnS3 has the Sn,S,-type structure with chains of SnS octa-hedra ; PbSnSeS is also known. l l 5c New chalcogenide halides including Sn,SI, Sn,SeI, and Sn,SBr, may be prepared by direct interaction of the components. SnC1,F2 is readily formed from SnCl and anhydrous HF; it reacts with fluorosulphuric acid to give SnF,(SO,F) .lo Sn,BrF5 contains an infinite tin(@ fluoride cationic network and free bromide ions; each tin atom has the typical tin(@ pyramidal co-ordination ;' Sn,Cl,' + dimer cations are present in ArSnCl(AlC1,) (Ar = C6H6 or p-xylene) and there is axially symmetrical interaction between the aromatic hydrocarbon and the tin."" Tin@) iodide has a new layer structure; two-thirds of the tin atoms are in SnC1,-like five-co-ordination and one-third are in PdC1,-like chains with octahedral co-ordination completed from other halogens.' lSc Pyramidal SnC1,- species are present in both forms of [Co(dpe),-ClISnC1 (dpe = Ph2PCH,CH,PPh2).' Mixed tin@) halides in particular the new SnBrC1 may be prepared from the component halides e.g.SnBr and SnCl , by the use of explosive shock compression."' SnC1 interacts with multiple carbon-carbon bonds as do SiF and carbenes; products of the type (36) are formed. Lead.-Pb and Pb can be trapped in matrices at 20K.122 Organolead thio-cyanates e.g. Me,PbNCS and Ph,Pb(NCS), have Pb-N bonds and are thus Many hexafluorostannates M"SnF have been described.'c =c-(36) R R ( a ) F. Vermont-Gaud-Daniel and J.-C. Jumas Compt. rend. 1972 275 C 741 ; (6) J.-C. Jumas M. Ribes and E. Philippot ibid. 1971 273 C 1356; (c) J.-C. Jumas, M. Ribes E. Philippot and M. Maurion ibid. 1972,275 C 269. F. Thevet N. H. Dung and C. Dagron Compr. rend. 1972,275 C 1279. R. Hoppe V. Wilhelm and N. Muller 2. anorg. Chem. 1972 292 1. 1 1 * ( a ) J. D. Donaldson and D. C. Puxley J.C.S. Chem. Comm. 1972 289; (b) M. S. Weininger P. F. Rodesiler A. G. Gash and E. L. Amma J . Amer. Chem. SOC. 1972, 94 2135; (c) R. A. Howie W. Moser and I. C. Trevena Acta Crysr. 1972 B28,2965. J. K. Stalick D. W. Meek B. Y. K. Ho and J. J. Zuckerman J.C.S. Chem. Comm., 1972,630.I2O S. S. Batsanov V. F. Lyakhova and E. M. Moroz Russ. J . Inorg. Chem. 1971,16,1233. l P. G. Harrison Inorg. Nuclear Chem. Letters 1972,8 5 5 5 . L. Brewer and C.-A. Chang J . Chem. Phys. 1972,56 1728 The Typical Elements 23 1 isothiocyanates. ' Triorganolead triazoles may be synthesized from tetra-organolead derivatives and l-chloro-1,2,3-triazoles.123b The reactions between N204 and tetra-alkyl-leads have been re-examined and shown to give organolead nitrates R,PbN03 and R,Pb(NO,),. 124 Polymeric Me,Pb(OR) derivatives result from the reaction between Me,Pb(C-CMe) and alcohols Me,PbX (X = OMe or NMe,) give trans-addition across the triple bond of CF,C-CCF . 25b Oxygen- and nitrogen-donor complexes of PhPbAc and Ph,PO complexes of diphenyl-lead halides have been described.' 26 Matrix-isolation studies on lead oxide vapours have identified the species PbO Pb,O (6 symmetry) and Pb404 (& symmetry) all similar to species observed with other Group IV element^.',^ A detailed study has been made on the thermal decomposition of lead dioxide. The system is very complex and depends upon the samples used but PbO Pb,O, Pbo1.55-1.40 and Pb12O19 (three forms) are formed.' 28 Cs,PbO contains five-co-ordinate lead(1v) ; the square-pyramidal units are joined together in :[PbO,,,O '3 chains. '29 Eight-co-ordinate lead is present in [Me,N] [Ph,PbAc,] ; the geometry is approximately hexagonal-bipyramidal with the phenyl groups in axial positions and each acetate bidentate.l3' The thermal decomposition of lead@) nitrate proceeds through the phases 2Pb0,Pb(N03) -+ 3PbO,Pb(NO,) -+ 4PbO,Pb(NO,) -+ PbO.' Thehydratedand basiclead(r1)oxidesformedfromNaOH and Pb(NO,), at 300 K have been very thoroughly investigated ;I3'' phases Pb(N03),,5Pb0,-$H,O and 3Pb(N0,),,7Pb0,5H20 have been identified.' '' Sulphur co-ordination about lead shows a wide variety of arrangements.Four-co-ordinate pyramidal monomers are found in Pb(S,CNEt,) and Pb[S,P(OEt),], whilst the isopropyl analogue Pb[S2P(OPri),] has very distorted six-co-ordina-tion approximating to a pentagonal bipyramid with a lone pair in an equatorial position. ' 3 2 b A distorted octahedral co-ordination by sulphur is also found in one form of Pb(thiourea) (ClO,),' 32c (the other form is eight-co-ordinate' 32d) ( a ) N. Bertazzi G . Alonzo A.Silvestri and G. Consiglio J. Organometallic Chem., 1972 37 281 ; ( 6 ) B. C. Pant and J. G. Noltes ibid. 1972 36 293. K. C. Williams and D. W. Imhoff J. Organometallic Chem. 1972 42 107. ( a ) R. J. Puddephatt and G. H. Thistlethwaite J.C.S. Dalton 1972 570; (b) R. J. Puddephatt and G. H. Thistlethwaite J. Organometallic Chem. 1972 40 143. l Z 6 H.-J. Haupt Z. Naturforsch. 1972 27b 724; H.-J. Haupt and F. Huber J. Organo-metallic Chem. 1971 33 175. "' J. S. Ogden and M. J. Ricks J. Chem. Phys. 1972 56 1658; c.f. D. W. A. Sharp, M. G. H. Wallbridge and J. H. Holloway Ann. Reports 1970,67 A 293 295. "* M. I. Gillibrand and B. Halliwell J. Inorg. Nuclear Chem. 1972 34 1143. P. Panek and R. Hoppe Z. anorg. Chem. 1972 293 13. ' 3 0 N. W. Allock J.C.S. Dalton 1972 1189.1 3 ' ( a ) E. V. Margulis M. M. Shokarev L. A. Sav'chenko L. I. Beisekeeva and F. I. Vershinina Russ. J. Inorg. Chem. 1972 17 21; ( 6 ) H. Brusset J. J. P. Martin C. Martin-Lefevre Y. Repelin E. Husson and B. Despagne Canad. J. Chem. 1972,50, 184; (c) J. J. P. Martin C. Martin-Lefevre and B. Despagne Bull. SOC. chim. France, 1972 2573; J. J. P. Martin C. Martin-Lefevre Y. Repelin and E. Husson ibid., p. 3341. 13' ( a ) H. Iwasaki and H. Hagihara Acta Crysr. 1972 B28 507; ( 6 ) Sr L. Lawlon and G. T. Kokotailo Inorg. Chem. 1972 11 363; ( c ) I. Goldberg and F. H. Herbstein, Acta Cryst. 1972 B28 400; (d) J. C. A. Boeyens and F. H. Herbstein Inorg. Chem., 1967,6 1408; ( e ) F. H. Herbstein and M. Kaftory Acta Crysr. 1972 B28 405 232 D. W. A . Sharp M. G.H. Wallbridge and J. H. Holloway and in Pb(thiourea) picrate,' 32e whilst tetragonal-prismatic co-ordination is present in $Pb(HC00),,4thiourea.' 3 3 Ammonium hexafluoroplumbate(Iv), (NH,),PbF, is formed from Pb(OAc) and hydrofluoric acid.'34 NaPbC1 is present in the vapour phase over heated NaCl-PbCl mixtures.' 35 2 GroupV Nitrogen.-Although in the gas phase atomic nitrogen reacts with organic compounds with carbonsarbon bond cleavage in condensed phases controlled insertion reactions appear possible and nitriles e.g. ClCH,CN from H,C= CC1 and amides e.g. CH,CONH from C,H50H are formed.'36b Further generalizations on hydrogen-bonding are now becoming apparent. In ammonium salts the co-ordination number can range from four to nine. When it is small, hydrogen-bonding is the most important aspect of the bonding from NH,'; when it is larger the ion is behaving as an alkali metal of size midway between the Rb+ and Cs+ ions.'37d Hydrogen-bonding appears to be responsible for the stability of the trans-rotamer of CF,CH,NH, which contains two potential hydrogen bonds.' 7 b Di-imine HNNH can be isolated as an unstable but pure material by thermal decomposition of alkali-metal toluene-p-sulphonylhydrazides M(Tos)NNH . 38 Pure anhydrous hydrazine is obtained by heating hydrazinium cyanurate in a vacuum.'39 N,(CF,) exists only in the gauche-form; in X2Y4 molecules an increased X-X bond length favours the trans-form as does increased electro-negativity of the substit~ents.'~~ Free hydrazoic acid may be obtained on an ion-exchange column ; it has been used to prepare hydrazinium azide N,H,N , i.e.N5H5 .141 H,NO- + H') of hydroxyl-amine has been determined as pK = 13.71 comparable with that ofmethan01.l~~ The molecular structure of (CF,),NOH shows a longer N-0 bond and a smaller ONC angle than in the radical (CF,),N0.'43a The mercurial [(CF,),NO],Hg reacts with CF,N CF to give {[(CF,),NOCF2](CF,)N},Hg which gives CF,N=C[ON(CF,),]OC[ON(CF,),I=NCF and CF,N=CFON(CF,) on The acid dissociation constant (for H2NOH 1 3 3 I . Goldberg and F. H. Goldstein Acta Cryst. 1972 B28 410. 1 3 4 R. L. Davidovich and T. A. Kaidalova Russ. J . Znorg. Chem. 1971 16 1354. 1 3 5 H. Bloom S. R. Richards and D . J. Williams Austral. J . Chem. 1972 25 2077. 1 3 b (a) J. J. Have1 and P. S. Skell J . Amer.Chem. SOC. 1972 94 1792; ( b ) C. T. Chen and N . N . Lichtin ibid. 1971,93 5922. 1 3 ' (a) A. A. Khan and W. H. Baur Acta Cryst. 1972 B28 683; (b) I . D. Warren and E. B. Wilson J . Chem. Phys. 1972,56,2137. 1 3 * N. Wiberg H. Bachhuber and G. Fischer Angew. Chem. Infernat. Edn. 1972,11,829. 1 3 9 E. Nachbaur and G. Leiseder Monarsh. 1971,102 1718. 140 J. R. Durig J. W. Thompson and J. D. Witt Znorg. Chem. 1972 11 2477. 1 4 1 G. Pannetier and F. Margineanu Bull. SOC. chim. France 1972 2617. 14* M. N . Hughes H. G. Nicklin and K. Shrimanker J . Chem. SOC. ( A ) 1971 3485. 143 ( a ) C . Glidewell C . J. Marsden A. G. Robiette and G. M. Sheldrick J.C.S. Dalton, 1972 1735; (b) R. E. Banks D. R. Choudhury R. N . Haszeldine and C. Oppenheim, J . Organomerallic Chem.1972 43 C20 The Typical Elements 233 heating.'43b The radical anion N,O- is formed in aprotic solvents on irradia-tion of N 2 0 with Gaseous HNO reacts immediately with NH to form NH,NO ; all of these species are present in polluted atmosphere^.'^^ Peroxonitrite can react to give both nitrite and nitrate as products; the metal-ion-catalysed self decomposition and reaction with peroxide both give nitrite as compared with isomerization to nitrate in alkaline solution.'46a The action of fluorine on NO2 gives the new fluoro-oxy-compound ONOF in low yield;'46b (CF,S),NH reacts with CF,SNCO or (CF,S),NC(O)NCO to give (CF,S)3N.'46' FS0,NCO reacts with alkali-metal fluorides in acetonitrile to give salts M [N( SO,F)C(O)F] . ' 466 NF4+BF4- has been prepared as have other salts of the NF4+ cation by irradiation of an NF,-BF,-F mixture.Irradiation at 77 K with excess fluorine gives a white solid which may be NF4+F-.14' BuN(F)NO, the first N-fluoro-nitramine may be synthesized by fluorination of aqueous alkali-metal salts of butylnitramine or by treating methyl-N-butyl-N-fluorocarbamate BuNFC02Me, with nitric A detailed phase study has been made on the N0,F-HF system ; from spectroscopic and conductivity measurements it is concluded that N0,F is completely dissociated to NO2+ and F- in this ~olvent.'~' The ClNCl bond angle in nitrogen trichloride is 107.1" consistent with the trends exhibited by PCl and AsC1 but much lower than that for the isoelectronic molecule N(SiH,),. It is concluded that there is little delocalization of the nitrogen lone-pairs on to the chlorine atoms.''' Phosphorus.-Traces of iodine catalyse the sublimation of red phosphorus. ' ' The structures of several phosphides have been described during the year [see p. 229 ref. 1111. Lip and Lip contain polymeric sheet anions involving P6 rings;'52a Sr,P, contains isolated PT3- units.'52b Diphosphine reacts with anhydrous hydrogen fluoride to give PH and polyphosphine (PH),; at high HF ratios H,PF is formed;'53 The P-P bond length in disphosphine is 0.026 A shorter than in Me,PPMe, a pattern similar to that in H,S2 as com-pared with Me,S2 but different from that of H6Si2 as compared with Me6Si,, where the bond lengths are almost Several new PH-containing com-144 S. P. Mishra and M. C. R. Symons J.C.S. Chem. Comm. 1972 510.1 4 s E. D. Morris jun. and H. Niki J. Phys. Chem. 1971,75 3193. 146 ( a ) M. N. Hughes and H. G. Nicklin J . Chem. SOC. ( A ) 1968 450; M. N. Hughes, H. G. Nicklin and W. A. C. Sackrule ibid. 1971 3722; (6) J. E. Sicre and H. J. Schu-macher 2. anorg. Chem. 1971,385 131 ; ( c ) A. Haas and R. Lorenz ibid. p. 33; (d) J. A. Rodriguez and R. E. Noftle Inorg. Chem. 1971 10 1874. 1 4 ' C. T. Goetschel V. A. Campanile R. M. Curtis K. R. Loos C. D . Wagner and J . N . Wilson Inorg. Chem. 1972 11 1696. 148 V. Grakauskas and K. Baum J. Org. Chem. 1972,37 334. 149 F. Seel and V. Hartmann J . Fluorine Chem. 197213 2 27 99. H. B. Burgi D. Stedman and L. S. Bartell J . Mof. Structure 1971 10 31. 5 1 H. Schafer and M. Trenkel Z . anorg. chem. 1971,391 1 1 . s 2 ( a ) H.-G.von Schneringand W. Wichelhaus Naturwiss. 1972,59,78; ( b ) W. Dahlmann and H.-G. von Schnering ibid. p. 420. F. Seel and K. Velleman Z . anorg. Chem. 1971,385 123. Holywell J. Struct. Chem. 1972 11 371. l S 4 B. Beagley A. R. Conrad J. M. Freeman J . J. Monaghan B. G. Norton and G. C 234 D. W. A . Sharp M . G. H . Wallbridge and J . H . Holloway pounds have been described. Hydrogen fluoride and water react with RPCl, to give phosphonous acid fluorides RP(H)(O)F' '" whilst pyramidal radicals HP02- HP03- and PO:- can be generated in aqueous solution by the action of Ti3 + and H 2 0 2 on hypophosphorous or phosphorous acids. '"' Detailed spectroscopic studies on HPF and H,PF confirm that hydrogen is present in the equatorial positions of trigonal bipyramids."'' H,PPF has a trans con-formation in the gas phase156a whereas Cl,PNMe is gauche with the PNC, portion of the molecular planar'56b (see p.232 ref. 140). Considerable interest continues to be taken in the geometry and mode of rearrangements of phosphorus particularly pentaco-ordinated phosphorus, compounds. Structural data on acyclic organophosphorus compounds published up to 1971 have been collected. Articles on pentaco-ordinated compounds include reference 157b. The structure of Ph,P=C=PPh has been determined and in crystallographically independent molecules the PCP angles are 144" and 1 30° of the same order of magnitude as in related molecules. ' Spectroscopic studies suggest that phosphabenzene C,H,P is planar. '"' The four-membered-ring compound (CF,PCF,) is formed from (CF,),PH and dimethylzinc ;l 59a phosphines and phosphites add to trifluoromethyl-substituted 2-aza-1,3-butadienes to give C-phosphorus derivatives e.g.R,P=C(Ph)CH= NCH(CF,) . l S g b Tris(carboxy)phosphines e.g. P(CO,R) are formed by the action of chloroformates on sodium phosphide. 160 Dimethylketen reacts with a variety of phosphines PXYZ to give compounds (37) which have trigonal-bipyramidal structures. 16'* P-OR' groups are readily converted into PR2 by use of R2X and NaA1H2(OCH,CH20Me)2.'6'b 1 5 5 ( a ) U. Ahrens and H. Falius Chem. Ber. 1972,105,3317; (6) A. L. J. Beckwith Austral. J. Chem. 1972,25 1887; ( c ) R. R. Holmes and C. J. Hora jun. Inorg. Chem. 1972,11, 2506. 156 ( a ) R. L. Kuczkowski H. W. Schiller and R. W. Rudolph Znorg.Chem. 1971 10, 2505; ( b ) J. R. Durig and J. M. Casper J. Phys. Chem. 1971,75 3837. 15' ( a ) L. S . Khaikin and L. V. Vilkov Russ. Chem. Rev. 1971,40 1014; (b) R. R. Holmes, Accounts Chem. Res. 1972,5 296; J. I. Musher J. Amer. Chem. Sac. 1972,94 5662; A. Rauk L. C. Allen and K. Mislow ibid. p. 3035; J. B. Florey and L. C. Cusachs, ibid. p. 3040; R. Hoffmann J. M. Howell and E. L. Muetterties ibid. p. 3047. ( a ) A. T. Vincent and P. J. Wheatley J.C.S. Dalton 1972 617; (b) R. L. Kuczkowski and A. J. Ashe tert. J. Mol. Spectroscopy 1972,42,457. 5 9 ( a ) D.-K. Kang and A. B. Burg J.C.S. Chem. Comm. 1972,763; (b) K. Burger J. Fehn, J. Albanbauer and J. Friedl Angew. Chem. Znternat. Edn. 1972 11 319. 160 A. W. Frank and G. L. Drake jun. J. Org. Chem. 1971,36 3461.1 6 1 ( a ) W. G . Bentrude W. D. Johnson and W. A. Khan J. Amer. Chem. SOC. 1972,94, 3058; (6) R. B. Wetzel and G. L. Kenyon ibid. p. 1774 The Typical Elements 23 5 Chloramines react with tertiary phosphines and arsines to give the correspond-ing amino-phosphonium and -arsonium chlorides e.g. [Ph,PNClR]Cl and [HN{ p,p'-(o-C,H,),}As(Me)NH,]Cl. 162 Cyclophosphamide hydrate (38) has a chair form ring with an equatorial amino-group and an axial phosphoryl oxygen ; this conformation about phosphorus is in contrast to that found for other systems without the amino sub~tituents.'~~ Wurtz coupling of F,PI and (CF,),PI or a redistribution reaction involving (CF,),PP(CF,) and P,F gives (CF,),PPF ; the PF group is basic to BH but the (CF,),P group does not appear to co-ordinate.164 Phenyl-lithium does not immediately completely cleave cyclo-polyphosphines but for example (EtP) gives Et(Li)P.PEt.PEt.P(Et)Ph ; the acylic derivatives are rapidly attacked by excess phenyl-lithium. ' 6 5 Cyclo-carbaphosphanes (PR'),(CRi) (n = 4 rn = 1; 11 = 3 m = 2) are formed from dihalides and potassium salts of cyclophosphides e.g. K,(PhP) with ClCH,.-CH,Cl gives (39).'66 In polar media biphosphines aggregate with formation of HlC-CH, I \ PhP\ P/PPh Ph (39) P-P donor-acceptor bonds. 67a Similar bonding is postulated in the adducts, e.g. [Et,PP(O)Cl,]Cl formed by phosphines and arsines and phosphoryl and thiophosphoryl halides. 67b Dimethylchlorophosphine reacts with NaOMe and NaSMe to give Me,PEMe ; Me,POMe rearranges slowly to Me,PO but Me,PSMe gives a stable phos-phonium salt which only gives Me,PS at 420 K.Me,POMe reacts with hydrogen chloride to give unstable [Me,P(H)OMe]Cl the thio-analogue may be present 1 6 * L. K. Krannich and H . H. Sisler Inorg. Chem. 1972 11 1226; S. E. Frazier and H. H. Sisler ibid. p. 1431 ; R. M. Kren and H. H. Sisler ibid. p. 2630. 1 6 3 J . C . Clardy J. A. Mosbo and J. G. Verkade J.C.S. Chem. Comm. 1972 1163. 164 H. W. Schiller and R. W. Rudolph Inorg. Chem. 1971 10 2500. 1 6 5 K. Issleib and F. Krech 2. anorg. Chem. 1971,385,47. I h 6 M. Baudler J. Vesper P. Junkes and H. Sandmann Angew. Chem. Internat. Edn., 1971 10 940; M. Baudler J. Vesper and H. Sandmann 2. Naturforsch. 1972 27b, 1007. 1 6 ' ( a ) H. C. E. McFarlane and W. McFarlane J.C.S. Chem.Comm. 1972 1189; ( b ) E. Lindner and H. Beer Chem. Ber. 1972 105 3261 236 D. W. A . Sharp M . G. H . Wallbridge and J. H. Holloway as an intermediate in the raction of Me,PSMe but decomposes to [Me,PH,]Cl and [Me,P(SMe),]Cl ; the latter compound decomposes.on heating to Me,P(S)-($Me). 68 Tetramethyl(methoxy)phosphorane Me,POMe and its homologues are readily formed from alcohols and trimethyl(methylene)phosphorane Me,P= CH ;169a Ph,POPh decomposes thermally to Ph,P and phenol whereas Ph,SbOR (R = alkyl) gives Ph,Sb ketones benzene and simple ethers in a very distinct reaction. '"' Phosphines Ar,P react with thionyl chloride initially by oxygen abstraction to Ar,PO and then through reaction with SC1 to give Ar,PC12 and Ar,PS; the corresponding arsines and stibines react to give for example Ar,AsCl by halogen transfer.' 7 0 Ph,P(O)OOP(O)Ph decomposes in chloroform to the unsymmetrical anhydride Ph,P(O)OP(O)(OPh)Ph. 17' 1,2-Oxaphosphetans e.g. (40) are formed by the reaction of electrophilic carbonyl OMe derivatives e.g. CF,COCF, with POR derivatives ;172a the ring system is bonded axial-equatorial in the trigonal bipyramid. EtPPh reacts with hexafluoroacetone to give (41a) which isomerizes to (41b) at 620 K ; both of the oxygen atoms in the latter compound are in apical positions with the ring 1 6 ' F. See1 and K.-D. Velleman Chem. Ber. 1972 105 406. 169 ( a ) H. Schmidbaur and H. Stiihler Angew. Chem. Infernat. Edn. 1972 11 145; (b) G. A. Razuvaev and N. A. Osanova J . Organometallic Chem. 1972,38 77. " O E. H.Kustan B. C. Smith M. E. Sobeir A. N. Swami and M. Woods J.C.S. Dalton, 1972 1327. l 7 I R. L. Dannley R. L. Waller R. V. Hoffman and R. F. Hudson J . Org. Chem. 1972, 37 418. 1 7 * (a) F. Ramirez G . V. Loewengart E. A. Tsolis and K. Tasaka J . Amer. Chem. Soc., 1972 94 3531; ( 6 ) Mazhar-ul-Haque C. N. Caughlan F. Ramirez J. F. Pilot and C. P. Smith ibid. 1971 93 5229; (c) D. D. Swank C. N. Caughlan F. Ramirez and J. F. Pilot ibid. p. 5236 The Typical Elements 237 axial-equatorial.' 7 2 b The oxygen atoms in (42) formed from Ph,POEt and tram-PhC(O)CH=CHC(O)Ph followed by treatment with p-bromobenzalde-hyde are also in apical positions.' 72c The phosphorinan ring in (43) has a flattened Ph 0 7 Ph P I4 chair conformation with the chlorine in an axial position.73 Four-co-ordinate phosphorus compounds (except OPF,) are protonated in sulphuric acid and oleum ; sulphonation occurs after protonation ' 74a fluorophosphoric acids are protonated in HS0,F and HS03F-SbF5 solutions. Fluorosulphuric acid even-tually fluorinates and protonated FH,PO is formed :l 74b [ClMe,P](CO),Mo is hydrolysed in the presence of base to Me,P(OH)Mo(CO) in which the hitherto unknown dimethylphosphorous acid is stabilized by co-ordination ; the P-Cl bond in the original complex is active and an extensive chemistry can be carried out whilst the phosphorus remains co-ordinated. 75 Organophosphorus derivatives containing P=O P=S etc. bonds have an extensive co-ordination chemistry which has been reviewed. 7 6 a Many examples of complexes containing these groups have been described including complexes of Ph,P(O)NMe PhP(O)(NMe,) ,l 76c Me,NP(O)NMeP(O)(NMe,) , OP(NMe,),,'76d R',P(0)OP(O)R2, RP(0)(NMe,)OP(O)(R)NMe,,'76' 1 7 3 L.Silver and R. Rudman Acta Cryst. 1972 B28 574. 1 7 4 (a) P. Haake and P. S. Ossip J. Amer. Chem. Soc. 1971 93 6918; G. A. Olah and C. W. McFarland Inorg. Chem. 1972,11 845. C. S. Kraihanzel and C. M. Bartish J. Amer. Chem. SOC. 1972,94,3572. 1 7 6 ( a ) N. M. Karayannis C. M. Mikulski and L. L. Pytlewski Inorg. Chim. Acta Rev., 1971 5 69; ( b ) M. W. G . de Bolster and W. L. Groeneveld Z. Naturforsch. 1972, 27b 759; ( c ) M. W. G. de Bolster and W. L. Groeneveld Rec. Trav. chim. 1971,90, 1153; (d) J.-M. Carpentier R. Schlupp and R. Weiss Acta Cryst. 1972 B28 1278; M. W. G. de Bolster and W.L. Groeneveld Rec. Trau. chim. 1972 91 171 185; ( e ) M. D. Joesten and Y. T. Chen Inorg. Chem. 1972,11,429; J . Inorg. Nuclear Chem., 1972 34 237; (f) J. Crea and S . F. Lincoln ibid. p. 1 1 31 ; (g) A. N. Pudovik A. A. Muratova M. D. Medvedeva and 8. G. Yarkova J. Gen. Chem. (U.S.S.R.) 1971, 41,771 ; A. N. Pudovik A. A. Muratova 8. G. Yarkova and MD. Medvedeva ibid., p. 1486; C. M. Mikulski N. M. Karayannis and L. L. Pytlewski J. Znorg. Nuclear Chem. 1972 34 1215; (h) 8. G. Yarkova I. Y. Kuramshin A. A. Muratova,* and A. N. Pudovik J. Gen. Chem. (U.S.S.R.) 1971 41 1008; (i) A. A. Muratova E. G. Yarkova I. Y. Kuramshin and A. N. Pudovik ibid. p. 1676; ( j ) A. A. Muratova, I. Y. Kuramshin 8. G. Yarkova and A. N. Pudovik ibid. p. 1984; (k) D. A. Wheat-land C.H. Clapp and R. W. Waldron Inorg. Chem. 1972 11 2340; (1) A. Miiller, V. V. K. Rao and P. Christophliemk J. Znorg. Nuclear Chem. 1972 34 245; S. V. Larionov and L. A. Il'ina J. Gen. Chem. (U.S.S.R.) 1971 41 767 238 D. W. A . Sharp M. G. H . Wallbridge and J. H. Holloway (Me0)3P0176f (in all the above complexes co-ordination is through the phos-phoryl oxygen) R' POR' and (EtO),P(O)Cl (adducts are formed with halides followed by isomerization of the ligand to R',R2P0 co-ordinated to the metal; in some cases there is elimination of alkyl halides followed by formation of compounds containing POM links),' 76g (RO),P(O)OH,' 76h (RO),PO(SH) (complexing through the phosphoryl oxygen),'76i (R0)2PS2-,'76i R' ,P(S)-XP(S)R2 ,' 7 6 k R,PSeS- ' 761 (in all of the above co-ordination is from sulphur), and (RO),POSe-.' 76m Hydrolysis of (MeO)P(O)(SMe)NH in alkaline solution takes place by P-0 bond cleavage whereas in acid solution the predominant cleavage is of P-S bonds.'77 PhP(O)Cl reacts with HIS in the presence of base to give [PhP(S)O], with oxygen in the ring.'78 The phosphinic acid (CF,),P(S)OH is formed by the action of sulphuric acid on salts of the acid ; it is a moderately strong acid which may be dehydrated to [(CF,),P(S)],O which undergoes nucleophilic attack to (CF,),P(S)X (X = NMe, F C1 or Br).17' A compound containing the (0)PSCN grouping (neopentyl-O),P(O)SCN is formed by the sequence R,P(O)-SCl -R2P(0)SCN.'80 CF,SSCF reacts with(CF3P),and(CF,),PP(CF,), to give (CF,S),PCF and CF,SP(CF,) respectively ; I 8 '' small-ring-containing phosphines and phosphites react with 3,4-bis(trifluoromethyl)-1,2-dithieten to give sulphur-containing phosphoranes e.g.(44). ' '' MePFCl and MePFBr may be prepared by cleavage of aminofluorophos-phines with hydrogen halide.'82 Addition of hydrogen fluoride to ylides e.g. Me,P=CH gives tetra-alkylphosphonium fluorides although molecular phosphoranes appear to exist for some of the compounds ;18,' sulphur chloride pentafluoride and CF300CF3 are mild fluorinating agents for the formation of L 7 7 17' J. J. Daly L. Maier and F. Sanz Helv. Chim. Acta 1972,55 1991. 1 7 9 A. A. Pinkerton and R. G. Cavell J . Amer. Chem. SOC. 1972 94 1870. I a o A. topusinski and J. Michalski Angew. Chem. Internat. Edn. 1972 11 838. l S L (a) I. B. Mishra and A.B. Burg Inorg. Chem. 1972 1 1 664; (b) N. J. De'ath and M. A. H. Fahmy A. Khasawinah and T. R. Fukoto J. Org. Chem. 1972,37 617. D . B. Denney J.C.S. Chem. Comm. 1972,395. H. W. Schiller and R. W. Rudolph Inorg. Chem. 1972,11 187. ( a ) H. Schmidbaur K.-H. Mitschke and J. Weidlein Angew. Chem. Internat. Edn., 1972,11 144; (b) C. J. W. Fraser M. E. McCartney D . W. A. Sharp and J. M. Win-field J . Inorg. Nuclear Chem. 1972 34 1455; (c) N. J. De'ath D . Z . Denney and D. B. Denney J.C.S. Chem. Comm. 1972,272 The Typical Elements 239 fluorophosphoranes ;183b*c it is suggested that (45) may have the ring diequatorial in one spectroscopically observable form. 83c Cyclopentadienylphosphorus difluoride C,H,PF prepared from KC,H and PBrF, shows fluxional behaviour.Silylphosphinimines and sulphur(v1) imides react with fluorophos-phoranes to give aminophosphonium fluorophosphates e.g. [R,P(N=PR,) - ,] + [R,PF,-J- ( n = 1 or 2). The hitherto unknown [Me,PF,]- is one product of these r e a ~ t i 0 n s . l ~ ~ (CF,),NCl gives both direct addition and addition of FCI (and elimination of CF,N=CF,) with trifluoromethylphosphorus halides e.g. (CF,),PCl gives (CF,),NP(CF,),Cl and (CF,),PCl,F. Alkoxyfluorophos-phoranes are stable when the alkyl group is electronegative e.g. CH,CCl, or is the neopentyl group. Bis(fluorophosphinothioy1)sulphides [RFP(S)],S are formed from PhPF and cyclodiphospha(v)thianes R(S)P(p,p'-S,)P(S)R. 8 8 Phospham (PN,H), gives salts with alkali-metal amides. lg9' Very many derivatives containing P-N bonds continue to be described ; in addition to these mentioned in the present section some will be found on p.244 under the head-ing of substituted phosphorus halides. Heating (MeNPF,) gives (MeNPF,) , for which a cubane-type skeleton is postulated [(MeN),P3F6] [PF,] and (MeN),-P,F7 ; for these two latter compounds cubane-type structures with one missing corner are postulated. 89b Many phosphinimine derivatives are now known. Me,P=NSiMe reacts with phosphorus chlorides to give substituted derivatives, e.g. (Me3P=N),P,l9'" and substituted disilanyl derivatives are formed from Me,P=NLi and for example Me,Si,Cl. l g o b Iminodichlorides e.g. PhN= P(NR,)Cl, react with symmetrical disubstituted ureas to give diphosphates e.g. [PhNHP(O) (NR,)] ,O. 90c Bisphosphimino derivatives e.g.[ClP(R I ) (R2)= NP(R3)(R4)Cl]Cl are formed from chlorophosphoranes and phosphinic thio-amides R,PSNH,. 90d Acetonitrile and phosphorus pentachloride react to 184 1 8 5 1 8 6 1 8 7 1 8 8 189 I 9 0 J. E. Bentham E. A. V. Ebsworth H. Moretto and D. W. H. Rankin Angew. Chem. Internat. Edn. 1972 1 1 640. W. Stadelmann 0. Stelzer and R. Schmutzler Z . anorg. Chem. 1971 385 142; R. Appel I . Ruppert and F. Knoll Chem. Ber. 1972 105 1492. H. G. Ang J . Fluorine Chem. 197213 2 181. D. V. Robert G. N. Flatau C. Demay and J . G. Riess J.C.S. Chem. Cumm. 1972, 1127. R. K. Harris J . R. Woplin M. Murray and R. Schmutzler J.C.S. Dalton 1972, 1590. ( a ) J. Goubeau and R. Pantzer 2. anorg. Chem. 1972 390 25; (b) K. Utvary and W. Czysch Monatsh. 1972 103 1048.( a ) W. Wolfsberger H. H. Pickel and H. Schmidbaur Z . Naturforsch. 1971 26b, 979; (6) H. Schmidbaur and W. Vornberger Chem. Ber. 1972 105 3187; (c) M. Bermann and K. Utvary Synrh. Znorg. Metal-org. Chem. 1971,1 171 ; (6) A. Schmid-peter N. Schindler and H. Eiletz ibid. 1972 2 187 240 D. W. A . Sharp M. G. H . Wallbridge and J. H . Holloway give [HCCl =C(NPCl ,) (PCl,)] [PCI,] whilst chloroacetonitrile gives HCCl= C(NPC1,)Cl. 1 9 ' Ph,PCH,PPh reacts with ammonia and carbon tetrachloride under pressure to give [Ph,P(NH,)N=P(Me)Ph,]Cl. Other biphosphines e.g. Ph,P(CH,),PPh give cyclic phosphonium salts (46) and the method provides (46) a good ,route to heterocyclic derivatives e.g. H,NX=NH and Ph,PCH,PPh, gives a XNPCPN heterocycle. 192 BCI and PCl react with ammonium chloride to give the phosphonitrilic precursor [Cl(Cl,P=N),PCl,] [BCl,].' 9 3 Mono-phosphazenes react with silazanes e.g. (Me,Si),NH to give compounds of the type SPF,N=PCl,NHSiMe which react further with PCI to give diphos-phazenes e.g. SPCl,N=PF,N=PCl SPCl,N=PCl,N=PCl,NMeSiMe, decomposes to the cyclic phosphazene (47). 194b Strong carboxylic acids hydrolyse CI P N* P a z II I sH \c1 (47) SPX,N=PX to SPX,NPH(O)X whilst weak acids e.g. acetic acid give SPX,NHC(O)CH derivatives. 194c Phosphinimines YN=PX (Y = MeSO,-, C1S02- or P,N,F,-) react with alcohols to give YN=PX,OR but these rearrange to YNRP(O)X with ether. 194d Ph,P(NH)N=P(NH,)Ph reacts with P(NMe,) with phosphonitrilic ring formation to give (48). ' 95 N Ph,P' +PPh, II I N /,N P / \ (48) Me,N H E.Fluck and W. Steck Z . anorg. Chem. 1972,387 349. 1 9 2 R. Appel R. Kleinstuck and K.-D. Ziehn Chem. Ber. 1972 105 2476. 193 K. Niedenzu I. A. Boenig and E. B. Bradley Z . anorg. Chem. 1972,393 88. * 9 4 ( a ) H. W. Roesky L. F. Grimm and E. Niecke Z . anorg. Chem. 1971 385 102; H. W. Roesky and W. Kloker Z . Naturforsch. 1972 27b 486; (6) H. W. Roesky, Chem. Ber. 1972 105 1439; ( c ) H. W. Roesky B. H. Kuhtz and L. F. Grimm Z . anorg. Chem. 1972,389 167; (d) H. W. Roesky and W. G. Bowing ibid. 1971 386, 191. 1 9 5 M. Bermann and J . R. van Wazer Inorg. Chem. 1972,11,209 The Typical Elements 24 1 Phosphazene particularly cyclophosphazene chemistry has been reviewed.'96 Phosphazenes can be reduced electrolytically to radical anions in non-aqueous media.19' Many structural studies on phosphazenes continue to be described. Amongst those which reveal new principles are the detection of two conformers at different temperatures for linear high-molecular-weight (NPF2) ; the low-temperature polymer has a cis,trans-planar chain conformation. ' 98a 2,2,4-C1 3-4,6,6-(NMe2),P,N has a distorted boat conformation with the 5-45 6-1 PN bonds longer than the others in the ring.'98b The difference in detailed geometry of two of the isomers of 2,4,6,8-Cl4-2,4,6,8-Ph4P4N4 suggests that steric factors are the most important influence on ring shape.'98' N,P,Brlo has a puckered ring (N,P,Cl is almost planar) with one re-entrant angle at a nitrogen atom. 198d A great deal of interest has been shown in the preparation of isomeric species, and many of the reactions involve formation of aminophosphazenes followed by replacement of the amino-group.P,N,F reacts with dimethylamine to give cis- and trans-1,3-P,N,F4(NMe,)21990 whilst P,N,Cl reacts with 8 moles of Me,NH to give trans-l,3-P,N,Cl,(NMe2)4 and some P,N,Cl(NMe,) . 199b P,N,Cl reacts with Me,NH to give various non-geminally substituted amino-phosphazenes. 199c The dimethylaminochlorides are fluorinated with SbF, preferentially at an amine-substituted phosphorus but total exchange of chlorine by fluorine can occur.199d Antimony trifluoride can substitute F for NMe in a non-geminal manner;'99e NMe can be substituted by C1 or Br (giving non-geminal isomers) by the action of hydrogen halide. 199s The reactions of P3N,F6 with amines diamines and hydrazines have been described ;'OO P,N,F,NH, (and SPF,NH2) react with boron chlorides to give derivatives such as (P,N3F,-NH),B ;"' isothiocyanatophosphazenes are prepared by the action of a thio-cyanate on the chlorophosphazenes in acetone.'02 NaON(CF,) gives phos-phazenes substituted by ON(CF 3)' groups.O3 A N4P ring compound (49) is formed from a succession of condensation reac-tion~.''~ The ring compound N~PCl,~NMe~BCl~NMe~PCl can be fluorinated 1 9 6 197 1 9 8 1 9 9 2 0 0 201 2 0 2 203 2 0 4 H. R. Allcock Chem. Rev. 1972,72 315. H. R. Allcock and W. J. Birdsall Inorg. Chem. 1971 10,2495. ( a ) H. R. Allcock R. L. Kugel and E. G. Stroh Inorg. Chem. 1972 11 1120; ( 6 ) F. R. Ahmed and D . R. Pollard Acta Cryst.1972 B28 513; (c) G. J . Bullen and P. A. Tucker J.C.S. Dalton 1972 1651 ; ( d ) J . G . Hartsuiker and A. J. Wagner ibid., p. 1069. ( a ) E. Niecke H. Thamm and D. Bohler Inorg. Nuclear Chem. Letfers 1972 8 261 ; (b) B. Green and D. B. Sowerby J . Inorg. Nuclear Chem. 1971 33 3687; ( c ) D . Millington and D . B. Sowerby J.C.S. Dalton 1972,2035; (4 B. Green D. B. Sowerby, and P. Clare J . Chem. SOC. ( A ) 1971 3487; ( e ) P. Clare D . Millington and D. B. Sowerby J.C.S. Chem. Comm. 1972,324; (f) P. Clare D . B. Sowerby and B. Green, J.C.S. Dalton 1972 2374. E. Niecke H. Thamm and G. Flaskerud Chem. Ber. 1971 104 3729; T. Chivers and R. Hedgeland Canad. J . Chem. 1972,50,1017. H. W. Roesky Chem. Ber. 1972,105 1726. R . L. Dieck and T. Moeller Inorg.Nuclear Chem. Letters 1972 8 763; T. Moeller and R. L. Dieck Synth. Inorg. Metal-org. Chem. 1972 2 19. P. 0. Gitel' L. F. Osipova and L. I . Kostikin J . Gen. Chem. (U.S.S.R.) 1971 41, 1416. A. Schmidpeter and K. Stoll Phosphorus 1971 1 103 242 D. W. A . Sharp M. G. H . Wallbridge and J. H. Holloway II \ N - N H (49) R2P p 2 with SbF or AsF without breaking the ring.205 Several examples of sulphur-containing rings have been described e.g. I(T-PCl,.N-SCl-N.PCl from S(N= S=O) and PC1 ,206a and also the corresponding sulphur(vI)=O compounds from O2 S(NH ,) and [Cl,P =NPC1 3] [PCl,] 06b or 0 S(N=PCI 3)2 and (Me Si) -NR,206c and sulphur(1v)-Me compounds.206d Isomers e.g. (50a b) are possible Me Ph P /fv\ PPh2 1 I 1 P ~ I ~ P / ~ \ P P ~ , II I1 (a) (50) in these systems,206e and related systems e.g.(NPCl,),NSOCl can be prepared by thermal decomposition of phosphinimine derivatives of sulphuryl chloride.206f Hydrogen sulphide reacts with phosphazene chlorides to give thiophosphamic acids [NP(SH),] ;,07 spirophosphoranes e.g ( 5 l) are formed from carboxylic R C / $ O N O N \c4 R (51) acid hydrazides and P(NMe,) .208 P(p,p',p''-[NMe],)P has planar PNNP links, suggestive of little n-bonding in the system.209 It seems probable that detailed 2 0 5 H. Binder Phosphorus 1972 1 287. 'Ob ( a ) H. W. Roesky Angew. Chem. Internat. Edn. 1972 11 642; (b) U. Klingebiel and 0. Glemser Z . Naturforsch. 1972,27b 467; ( c ) U. Klingebiel and 0. Glemser Chem. Ber. 1971 104 3804; 1972 105 1510; (d) R. Appel and K.-W.Eichenhofer ibid., p. 3859; ( e ) M. Bermann and J. R. van Wazer Inorg. Chem. 1972,11,2515; (f') H. H. Baalmann H. P. Velvis and J. C. van de Grampel Rec. Trau. chim. 1972 91 935. '07 B. Yanik and V. Zheshutko J . Gen. Chem. ( U . S . S . R . ) 1971 41 2668. ' 0 8 A. Schmidpeter and J. Luber Angew. Chew. Internat. Edn. 1972 11 306. * 0 9 W. vanDoorne G. W. Hunt R. W. Perry and A. W. Cordes Inorg. Chem. 1971, 10 2591 The Typical Elements 243 packing considerations greatly affect the geometry of many of these cyclic mole-cules. The monoclinic form of [O,P(NMe,),] has all exocyclic oxygens on one side of a chair-form ring whilst the orthorhombic form has two oxygens on one side of the ring which is planar except for one phosphorus atom.210 The action of sulphur on P4(NMe) gives adducts P4(NMe),S (n = 1-3) [P4(NMe)6S4 is also known] which appear to retain the P,(NMe) skeleton.2' ' Dimethylamino-chlorophosphines react with antimony pentachloride to give aminochlorophos-phonium salts e.g.[Me2NPCl,] [SbCl,]. l 2 Oxidationofphosphateanions in solution gives the radicals'P0,2-,'P020H-, 'HP02- and 'PhP02-.213 The use of 32P labelling shows that Up to fifteen different oxy-anions of phosphorus can be separated on an ion-exchange resin.214 Orthophosphoric acid in NNN'N'-tetramethylurea condensed with excess of a carbodi-imide gives a mixture of cyclic ultraphosphates. Hydrolysis yields cyclic metaphosphates (MPO,) to (MPO,),, and samples of the new compounds (NaPO,) (x = 5,7 or 9) were isolated.21 Neutral hypodiphosphorous esters e.g.C,H4O2P-PO2C6H4 are formed from the phosphorochloridite and sodium.21 In CuLi(PO,) infinite twisted (PO,) chains are pre~ent,~' 7a whilst BaNaP,O, contains P30 rings in a chair configuration217b and a P@15 ring anion is present in Na4NH4P5015,4H20.217c The anion in Na,P,O is in an eclipsed configuration with a POP angle of 127" ;,' 7d spectroscopic studies suggest that in sodium hypophosphates the H2P2062- anion is in an eclipsed configuration whilst it is in a staggered configuration in potassium Salk2 ' 7e The ester confor-mation in AgPO,(OEt) is syn-clina1,anti-clinal whereas in the barium salt the conformation has been found to be syn-clina1,syn-clinal. Various new peroxyphosphoric acids have been described. OP(OH)(OOH), is formed from P4010 P203Cl4 or OPC12(OH) and H202 whilst P203F4 reacts with H 2 0 2 to give OPF,(OOH).OPC1,F reacts with H 2 0 2 to give OPF(OH)(OOH).218 Sulphatophosphates e.g. [P04S0,]3- are formed from chlorosulphuric acid and phosphates in nitromethane. Triethylammonium 2 1 0 V. I . Andrianov N . G. Bokii V. D. Cherepenskii-Malov B. L. Tarnopol'skii and Yu. T. Struchkov Zhur. strukt. Khim. 1969 10 866; V. D. Cherepenskii-Malov, A. I . Gusev I. A. Nuretdinov and Yu. T. Struchkov ibid. 1971 12 126. 2 1 1 J. G. Riess and A. Wolff J.C.S. Chem. Comm. 1972 1050; c.f. R. R. Holmes and J. A. Forstner Znorg. Chem. 1963 2 377. 2 1 2 K. Press1 and A. Schmidt Chem. Ber. 1972 105 3518. 2 1 3 B. C. Gilbert J. P. Larkin R. 0. C. Norman and P. M. Storey J.C.S. Perkin ZZ, 1972 1508. 2 ' 4 M.Tominaga T. Nakamura and S. Ohashi J . Inorg. Nuclear Chem. 1972 34 1409. 'I5 T. Glonek J . R. van Wazer M. Mudgett and T. C. Myers Znorg. Chem. 1972 11, 567. ' 1 6 E. E. Nifant'ev A. I. Zavalishina and I . V. Komlev J . Gen. Chem. ( U . S . S . R . ) 1971, 41 1457. '17 (a) M. Laugt I. Tordjman J. C. Guitel and M. Roudaut Acta Cryst. 1972 B28, 2352; ( b ) C. Martin and A. Mitschler ibid. p. 2348; ( c ) K. H. Jost ibid. p. 732; (6) K. J . Leung and C. Calvo Canad. J . Chem. 1972 50 2519; ( e ) P. Klima J. Stejskal, and B. Hajek Specrrochim. Acta 1972 28A 1909; (f) J. P. Hazel and R. L. Collin, Acta Cryst. 1972 B28 2951 ; c.f. Y . Kyogoku and Y. Iitaka ibid. 1966 21 49. ' I 8 E. Fluck and W. Steck Z . anorg. Chem. 1972,388 53. 2 1 9 J.-C. Fischer G. Palavit M.Wartel and J. Heubel Compt. rend. 1972 274 C 867 244 D. W. A . Sharp M. G. H . Wallbridge and J. H. Holloway tris-(0-phenylenedioxy)phosphate(v) formed from catechol and tris-(0-phenyl-enedioxy)cyclotriphosphazene contains an octahedrally co-ordinated phosphorus atom. O Lead thiolates are good reagents for preparing thiophosphates and thio-phosphites;221 the conformation of the ester groups in K,S,P(OCH,C,H,) is syn-clinal anti-periplanar. 2 2 Various trifluoromethyl phosphates thiophos-phates and thiophosphites (CF3),PS2- (CF3),PSO- CF3P02- CF3PS202-, CF3PS022- CF3P03,- CF,PS,OH- CF,PSO,H- and CF3P(H)02- are formed by hydrolysis of trifluoromethylphosphorus-sulphur or -oxygen deriva-t i v e ~ . ~ ~ The existence of tetrahedral fluoroxyphosphate anions has been confirmed in the salts CaP03F,2H,0 (NH4),P0,F,H20 and (NH4),P0,F,-H,O.24 The structures of several halogenophosphorus pseudohalides have been described. In PF,CN the cyanide is tilted away from the f l u o r i n e ~ . ~ ~ ~ ' F,PNCO and F,PNCS have bent NCX units (see p. 215 ref. 8b) with the pseudohalide group trans to the bisector of the FPF angle,225b an arrangement similar to that in F,PN C NPF (prepared from F2PBr and Ag2CN,).225C The chlorine atoms in phosphorus chloride fluorides are readily exchanged for azide by use of sodium azide in various solvents.226 The nitrogen atom in PF,NH appears to be planar PF4NH2 may be prepared by the vapour-phase reaction between PF4C1 and ammonia.227b >NH groups readily undergo substitution into phos-phorus halides or the substitution may be effected indirectly by use of silylamines ; amongst compounds containing P-N bonds are hydrazine,228"* NSCC13,228C and S3N3228d derivatives.[Cl,P(O)],NMe undergoes multiple substitution by dimethylamino-groups ; the bis-compound is the non-geminal isomer. [Cl,P(S)],NR and Cl,PS-NR.PCl are formed from (Cl,P),NR and sulphur; on heating they eliminate PCl and give cyclodiphosphazenes ; [RNP(S)Cl] 0 Cl,P(S).NR-P(O)CI and [Cl,P(S)],NR can be prepared by condensation reac-t i o n ~ . ~ ~ ~ ~ Substitution of Me,N into Cl,P(O)NMePCl occurs first at the phosphorus(II1) atom but there is subsequent interchange to the phosphorus(v), 2 2 0 H. R. Allcock and E. C. Bissell J.C.S. Chem. Comm. 1972 676. 2 2 1 R. A. Shaw and M. Woods Phosphorus 1971,1,41 191.2 2 2 J. P. Hazel and R. L. Collin Acta Cryst. 1972 B28,2279. 223 A. A. Pinkerton and R. G . Cavell Inorg. Chem. 1971 10 2720. 2 2 4 A. Perloff Acta Cryst. 1972 B28,2183; A. F. Berndt and J. M. Sylvester ibid. p. 2191. 2 2 5 ( a ) P. L. Lee K. Cohn and R. H. Schwendeman Inorg. Chem. 1972 11 1917; (b) D. W. H. Rankin and S . J. Cyvin J.C.S. Dalton 1972 1277; ( c ) D. W. H. Rankin, ibid. p. 869. 2 2 6 S. R. O'Neill and J. M. Shreeve Inorg. Chem. 1972 11 1629; E. L. Lines and L. F. Centofanti ibid. p. 2269. 2 2 7 ( a ) A. H. Brittain J. E. Smith P. L. Lee K. Cohn and R. H. Schwendeman J. Amer. Chem. Sac. 1971 93 6772; (b) A. H. Cowley and J. R. Schweiger J.C.S. Chem. Comm. 1972 560. 2 2 8 ( a ) H. W. Roesky and 0. Petersen 2. Naturforsch. 1971,26b 1232; (b) M.D. Havlicek and J. W. Gilje Inorg. Chem. 1972 11 1624; H. W. Roesky W. Schaper and S. Tutkunkardes 2. Naturforsch. 1972. 27b 620; (c) H. W. Roesky and L. F. Grimm, Angew. Chem. Internat. Edn. 1972 11 642. 229 ( a ) I . Irvine and R. Keat J.C.S. Dalton 1972 17; (b) R. Keat ibid. p. 2189; ( c ) R. Keat Phosphorus 1972 1 253 The Typical Elements 245 and substitution of two NMe groups can give two isomers Cl(Me,N)P(O)-NMePClNMe and (Me,N),P(O)NMePCl .22 9c Fluoroisocyanatophos-phorus(v) derivatives e.g. (OCN),P(S)F are best prepared by fluorinating for example SP(NCO) with antimony trifluoride.,,' Fluoroaminophosphines form P + B bonds with borane fragments and N -+ B bonds with boron tri-f l ~ o r i d e . " ~ ~ ~ ~ ~ The compound (52) reacts with excess of BF to give [ MehCH,CH,( Me)NP] + [B2F7] - .Me (52) The thermally unstable complexes PX,,NMe (X = C1 or Br) appear to have trigonal-bipyramidal structures with an equatorial lone pair and axial nitrogen atoms. 32 Thiophosphoric esters containing P(S)(OR) groups give P(0)Cl groups with chlorine in a general reaction.233 All of the chlorobromophos-phonium ions [PCl,Br,-,]+ (0 < n < 4) have now been identified.234 Previous structural studies on hexafluorophosphoric acid hydrate appear to have been erroneous and the composition is now considered as H30+PF6-,HF,4H20.235 Arsenic.-Studies of the interaction of ASH, a strong catalyst poison with metal surfaces show ASH ASH, and ASH as surface species; oxidized films appear to give arsenic The C,As ring of 2,3,6-triphenylarsenin is planar.237 1-Arylarsoles (53) give firstly a radical anion with alkali metals and As I R (53) then give metal arsenides by cleavage of the R-As bond;238" the arsenic can be oxidized to arsenic(v) with chlorine (from PhICl ,) or h y p ~ c h l o r i t e .~ ~ ~ ' (4-Me2-NC,H,),M (M = As or Sb) are oxidized to blue Ar3M2+ cations with PhIC12.238c 230 V. A. Shokol and L. I. Molyavko J . Gen. Chem. (V.S.S.R) 1971,41 1412. 231 S. Fleming and R. W. Parry Inorg. Chem. 1972 11 1,2534. 232 D. H. Boa1 and G. A. Ozin J.C.S. Dalton 1972 1824. 233 W. Haubold and E. Fluck Z . anorg. Chem. 1972,392 59. 234 K. B. Dillon and P. N. Gates J.C.S. Chem. Comm. 1972 348. 2 3 5 D. W. Davidson and S. K. Garg Canad. J . Chem. 1972,50 3515. 2 3 6 I .M. Al-Daher and J. M. Saleh J . Phys. Chem. 1972 76 2851. 2 3 7 F. Sanz and J. J. Daly Angew. Chem. Internat. Edn. 1972,11 630. 2 3 8 ( a ) G. Markl and H. Hauptmann Angew. Chem. Internat. Edn. 1972 11 439; (b) G. Markl and H. Hauptmann ibid. p. 441 ; (c) J.-M. Keck and G. Klar Z . Naturforsch., 1972,27b 591 596 246 D. W. A . Sharp M. G. H . Wallbridge and J. H . Holloway The barrier to inversion in arsenic compounds is appreciably greater than that in ph~sphines.~~’ Organoarsenic azides are formed from other halides and lithium a~ides.’~~‘ There is some spectroscopic evidence for association of these compounds probably through bridging azide Sulphur silylimides react with organo-arsenic halides to give heterocyclic compounds e.g. (54), containing As S and N.241 Tetramethyldiarsenic disulphide in solution under-goes the equilibrium Me,AsSSAsMe 2 Me,As(S)SAsMe, although in the solid state the AsV-As”’ structure is stabilized ;242a Ph,As,S is a ring compound with a non-planar AsSAsSS ring.242b Dithioarsenates e.g.M~,AsS,M,~~ (from hydrogen sulphide and sodium cacodylate) and P ~ A s S M ~ ~ (from Ph2As02K and hydrogen sulphide) form salts with most metals. Me,NAsCl is present as the trans-form at room temperature but is partially converted into a second isomer probably the gauche-form at lower tempera-t u r e ~ ~ ~ ~ (see p. 232 ref. 140). AsOCl and As40sC1 are formed in the AsCl,,As,O, system.246 Ca(H,AsO,) contains symmetrical hydrogen bonds.247 The arsenite complex of dithiothreitol(55) has a pyramidal arsenic atom common to three rings (56).248 Vrbaite H ~ T ~ A S ~ S ~ S ~ contains As2SbSs chains and Hg3As4S sheets ;249 it is the first material to contain mixed (As Sb) chains.-CH,SH :*:: CH,SH S - 4 0 H Ai0> ‘S 239 G. H. Senkler jun. and K. Mislow J. Amer. Chem. SOC. 1972 94 291. 2 4 0 ( a ) D. M. Revitt and D. B. Sowerby J.C.S. Dalton 1972,847; (b) W. Beck W. Becker, K. F. Chew W. Derbyshire N. Logan D. M. Revitt and D. B. Sowerby ibid. p. 245. 2 4 1 0. J. Scherer and R. Wies Angew. Chem. Internal. Edn. 1971 10 812; 1972 11 529. 2 4 2 ( a ) R. A. Zingaro K. J. Irgolic D. H. O’Brien and L. J. Edmonson jun. J. Amer. Chem. Soc. 1971,93 5677; (b) A. W. Cordes P. D. Gwinup and M. C. Malmstrom, Inorg. Chem. 1972 11 836. 2 4 3 W. Kuchen M. Foster H. Hertel and B.Hohn Chem. Ber. 1972 105 3310. 2 4 4 A. Miiller and P. Werle Chem. Ber. 1971 104 3782. 2 4 5 J. R. Durig and J. M. Casper J. Mol. Structure 1971 10 427. 2 4 6 P. Flogel Z. anorg. Chem. 1972,389 188. 2 4 7 G . Ferraris D. W. Jones and J. Yerkess J.C.S. Chem. Comm. 1971 1568. 2 4 8 W. B. T. Cruse and M. N. G. James Acta Cryst. 1972 B28 1325. 2 4 9 M. Ohmasa and W. Nowacki Z. Krist. 1971 134 360 Thu Typical Elements 247 Antimony.-Sb-C bond cleavage occurs on treatment of alkylaryl-stibines with sodium; the reaction is useful for the subsequent formation of s t i b i n e ~ . ~ ~ ~ Bond cleavage also occurs when pentamethylantimony is treated with acids ; the resultant pseudohalides appear to be ionic but carboxylates seem to have chelat-ing carboxy-groups in the solid;250b Ph,BiNO and Ph4Bi02CC1 seem to be molecular solids.250' The compounds (Ph,SbN,),O and (Ph,BiC104)20 have metal-oxygen-metal bridges and trigonal-bipyramidal co-ordination about the metal; the previously described salts (R,M),0(C104) (M = Sb or Bi) all pre-sumably have comparable structures2 The halogeno-organo-antimony acetylacetonates have octahedral co-ordination about antimony in the solid state [the structures of MeSbCl,(a~ac)~~~" and P h S b C l ( a ~ a c ) ~ ~ ~ ~ have been determined] ; isomers are present in solution the various species presumably resulting from the relative co-ordination positions in the ~ctahedron.~ 2c Thermally stable R' Sb(OR2) compounds have been prepared by the sequence R',SbBr + Br -+ R',SbBr NaoR2 +RI2 Sb(OR2),; the compounds appear to be octahedral with bridging (methoxy) or chelating (OAc) Bisper-oxides Ph,Sb(OOR) are formed by the action of hydroperoxides on Ph,Sb.254 SbC14N is dimeric with bridging through one nitrogen of each of two linear azide The SbP molecule is present in the gas phase above heated mixtures containing the component elements.256 Dehydration of antimonic acid cannot be effected without some reduction of the metal and phases Sb6013 (with a defect pyrochlore structure) and /?-Sb204 are formed.257 Antimony pentachloride reacts with acid chlorides to give either ionic species involving chloride ion transfer to SbCl or co-ordination compounds involving 0 -+ Sb bonding.Structures describing these types of interaction include p-CH3-C6H4. COCl,SbCl (two forms one ionic and one m01ecular),~~~" CH,COCl,SbCI ,258b ( a ) S.-I.Sato Y . Matsumura and R. Okawara Inorg. Nuclear Chem. Letters. 1972, 8 847; J. Organometallic Chem. 1972 43 333; ( b ) H. Schmidbaur K.-H. Mitschke, J. Weidlein and S . Cradock Z . anorg. Chem. 197 1 386 139 ; H. Schmidbaur K.-H. Mitschke and J. Weidlein ibid. p. 147; ( c ) R. E. Beaumont and R. G. Goel Inorg. Nuclear Chem. Letters 1972 8 989. G. Ferguson R. G. Goel F. C. March D. R. Ridley and H. S. Prasad J.C.S. Chem. Comm. 1971 1547; R. G . Goel and H. S. Prasad Inorg. Chem. 1972 11 2141; J . Organometallic Chem. 1972 36 323. 2 5 2 ( a ) N. Kanehisa Y . Kai and N. Kasai Inorg. Nuclear Chem. Letters 1972 8 375; ( b ) K. Onuma Y. Kai and N. Kasai ibid. p. 143; ( c ) H. A. Meinema and J. G.Noltes, J. Organornetallic Chem. 1972,37 C3 1 ; H. A. Meinema A. Mackor and J. G. Noltes, ibid. #. 285; N. Nishii and R. Okawara ibid. 1972 38 335. 2 5 1 2 5 3 H. A. Meinema and J. G. Noltes J . Organometallic Chem. 1972 36 313. 2 5 4 G . A. Razuvaev T. G. Brilkina E. V. Krasilnikova T. I. Zinovjeva and A. I. Filimonov, 2 5 5 2 5 6 J. Kordis and K. A. Gingerich J . Phys. Chem. 1972,76 2336. 2 5 7 D. J. Stewart 0. Knop C. Ayasse and F. W. D. Woodhams Canad. J . Chem. 1972, 50 690. 2 5 8 ( a ) B. Chevrier J.-M. Le Carpentier and R. Weiss J . Amer. Chem. SOC. 1972 94, 5718; ( b ) J.-M. Le Carpentier and R. Weiss Acta Cryst. 1972 B28 1421 ; ( c ) J.-M. Le Carpentier and R. Weiss ibid. p. 1430; ( d ) B. Chevrier J.-M. Le Carpentier and R. Weiss ibid. p. 2673; ( e ) B.Chevrier J.-M. Le Carpentier and R. Weiss ibid. p. 2667; (f) J.-M. Le Carpentier and R. Weiss ibid. p. 1442; (8) H. Kietaibl H. Vollenkle, and A. Wittmann Monatsh. 1972 103 1360. J. Organometallic Chem. 1972 40 15 1 . U. Miiller Z . anorg. Chem. 1972 388,207 248 D. W. A . Sharp M. G. H. Wallbridge and J. H . Holloway (CH,),CHCOCl,SbCl ,258c and o-CH ,.C6H,-COC1,SbCl 258d (all ionic), PhCOCl,SbCl, m-CH,.C,H,.COCl,SbCl (CH2COC1)2,2SbC1,258J and C,Cl,O,CO,SbCl 58g (all molecular). K2Sb,S7 contains flat SbS pyramids and polymeric four-co-ordinate units based on trigonal-bipyramidal co-ordination with an equatorial lone pair and polymerization through the axial sulphur atoms.,, Dithiolate complexes of antimony(rI1) and bismuth(Ir1) are readily formed ; the bismuth complexes are dimeric probably with dithiolate bridges.,,’ Trimeric and dimeric species are observed by mass spectroscopy over antimony pentafluoride.26’ An accurate structure determination on (NH4)2SbF shows square-pyramidal anions ;262n the anion in CsSb2F7 consists of two trigonal bipyramids (each having an equatorial lone pair) joined by an axial bridge.,,,’ SbCl,F is ionic having the structure [SbCl,] [F,ClSbFSbClF,] ;263u Sb,Cl,F, (from an SbC1,-SbF melt) is [SbCl,] [Sb2F 1].263b a-Cs,Sb,Cl is similar to the corresponding arsenic chloride and contains SbC1 pyramidal molecules and chloride ions.264 Chlorobromoantimonates(v) are readily formed e.g. Et,NBr and SbCl gives Et,NSbC15Br.265 [Me,N],Sb,Br contains Sb,Br,,- anions bridged by Br molecules; each Sb,Br unit consists of two SbBr octahedra sharing a face.,,, Bismuth.-KBiO has chain anions ~[Bi0,,,0,,,].267 Co-ordination arrange-ments about bismuth are frequently complex.Bis-( 1-oxopyridine-2-thio1ato)-phenylbismuth(II1) has square-pyramidal co-ordination with the lone pair presumably occupying the position trans to the phenyl group.268a In trichlorotris-(3-sulphanilamido-6-methoxypyridazine)bismuth(111) co-ordination is from three chlorines three nitrogens and three oxygens and the position of the lone pair is not obvious.268b A new phase LiBiSe is formed by direct reaction of the component elements Bi,In,S contains six- and seven-co-ordinate bismuth, and the indium atoms are in octahedral ~o-ordination.~~~’ MBi,Te (M = Pb, Sn or Ge) SnBi,Te, and SnSb,Te have layer lattices.269c Bismuth trichloride also has a complex co-ordination sphere about bismuth consisting of a distorted 2 5 9 H.A. Graf and H. Schafer Z . Naturjorsch. 1972 27b 735. 2 6 0 G. Hunter J.C.S. Dalton 1972 1496. 2 h 1 M. J. Vasile and W. E. Falconer Inorg. Chem. 1972 11 2282. ( a ) R. R. Ryan and D. T. Cromer Inorg. Chem. 1972 11 2322; ( 6 ) R. R. Ryan, S. H. Mastin and A. C. Larson ibid. p. 2793. 2 h 3 ( a ) H. Preiss Z . anorg. Chem. 1972 389 254; (6) H . B. Miller H. W. Baird C. L. Bramlett and W. K. Templeton J.C.S. Chem. Comm. 1972 262. 2 6 4 K. Kihara and T. Sudo Z . Krist. 1971 134 142. 2 6 5 C. J . Adams and A. J . Downs J. fnorg. Nuclear Chem. 1972,34 1829; F. F. Bentley, 2 h 6 C. R. Hubbard and R. A. Jacobson Inorg. Chem. 1972 11 2247.2 6 7 B. Schwedes and R. Hoppe Z . anorg. Chem. 1972,392 97. 2 6 8 ( a ) J. D. Curry and R. J. Jandacek J.C.S. Dalton 1972 1120; (6) M. B. Ferrari, L. C. Capacchi L. Cavalca and G. F. Gasparri Acta Cryst. 1972 B28 1169. 2 6 9 ( a ) S . I . Berul’ V. B. Lazarev and A. V. Salov Russ. J . Inorg. Chem. 1971 16 1779; (bJ G. Chapius C. Gnehm and V. Kramer Acta Cryst. 1972 B28 3128; ( c ) T. B. Zhukova and A. I. Zaslavskii Soviet Phys. Cryst. 1972 16 796. 2 6 2 A. Finch P. N. Gates and F. J . Ryan fnorg. Chem. 1972 11 413 The Typical Elements 249 trigonal pyramid with bridging to five other chlorine atoms ;270a the geometry about bismuth in Cs2NaBiC1 appears to be Part 111 Groups VI-VIII 1 GroupVI Oxygen.-Useful reviews concerning observed and predicted spectral data for 02 Oz- 02+ and OtZ+,la polycations of Group VI,Ib oxygen fluorides and dioxygenyl compounds l C complexes of oxygen,' and complexes of oxygen-containing ligands ' have been published.The kinetics of the reactions 0 + 0 -+ 2OZ2" and 0 + NOZ -P NO + 0,2b have been studied. The second investigation illustrated the value of atomic resonance fluorescence spectrometry for determining rate constants of rapid atom + molecule bimolecular reactions. The existence of 02- as well as doubly charged halogen Te and Bi anions has been dempstrated by magnetic and electric deflection methods., Electron affinities for oxygen4- and ozone4" have been measured. Because of the difficulties associated with such measurements there is a notably long history of oxygen electron-affinity determinations.The recently determined values vary only a little and there is good agreement for a lower limit of 0.45 & 0.1 eV.4d The reaction of molecular oxygen with ground-state sulphur atoms has been investigated in the vacuum-ultraviolet region'" and by the flash photolysis-resonance fluorescence technique which suggests that the S(3P) atom attacks the Oz(3C) molecule end-on to form SOO which then rapidly falls apart to give SO(,C) and O(3P).56 The photochemistry of atmospheric ozone has been reviewed.6 The ozonide ion (03-) obtained by X-ray irradiation of l70-enriched KClO, has been studied by e.s.r. and the 1 7 0 hyperfine splittings observed have been tentatively interpreted to indicate slight distortion of the molecule from C2r to C symmetry.'" "* ( a ) S .C . Nyburg G. A. Ozin and J. T. Szymanski Acta Cryst. 1971 B27 2298; ( 6 ) L. R. Morss and W. R. Robinson ibid. 1972 B28 653. ' ( a ) P. H . Krupenie f . Phys. Chem. Ref. Data 1972 1 423; ( b ) R. J. Gillespie and J. Passmore Accounts Chem. Res. 1971,4,413; see also R. J. Gillespie and J. Passmore, Chem. in Britain 1972 8,475; (c) I. V. Nikitin and V. Ya. Rosolovskii Uspekhi Khim., 1971 40 1913; ( d ) J. A. McGinnety in 'MTP Internat. Rev. Sci. Inorg. Chem. Ser. One' 1972 5 229 ed. D. W. A. Sharp Butterworths London 1972; ( e ) S. M. Nelson, ibid. p. 175. (a) J. L. McCrumb and F. Kaufman f . Chern. Phys. 1972,57 1270; ( b ) M. A. A. Clyne and H. W. Cruse J.C.S. Faraday ZZ 1972 68 1281. K. Bethge Umschau 1972,72 23. (a) J. Berkowitz W.A. Chupka and D. Gutman f . Chem. Phys. 1971 55 2733; ( b ) R. J. Celotta R. A. Bennett J. L. Hall M. W. Siegel and J. Levine Phys. Reu. ( A ) , 1972 6 631; (cj S. J. Nalley and R. N. Compton Chem. Phys. Letters 1971 9 529; ( d ) T. 0. Tiernan B. M. Hughes and C. Lifshitz J . Chem. Phys. 1971,55 5692. ( a ) R. J. Donovan and D. J. Little Chem. Phys. Letters 1972 13,488; ( 6 ) D. D. Davis, R. B. Klemm and M. Pilling Internat. f . Chem. Kinetics 1972 4 367. H. U. Diitsch Adu. Geophys. 1971,15 219. Chem. Phys. Letters 1972 14 518. ' ( a ) S . Schlick f . Chem. Phys. 1972 56 654; ( b ) M. E. Jacox and D. E. Milligan 250 D. W. A . Sharp M. G. H . Wallbridge and J. H. Holloway A valence angle of 110 & 5" in 03- produced by the reaction of 0- with O2 in an argon matrix has been reported and absorptions near 1000 cm- ' have been attributed to trans-O,-." Evidence for the existence of bound-state dimers including (O,), has been reviewed and new insights into the nature of weak intermolecular interactions have been discussed.* HO, which is an important intermediate in many reaction systems in radiation chemistry photochemistry atmospheric chemistry and in combustion and other thermal reactions has been observed in the flash photolysis of H,O vapour and 0,-H mixture^.^" The molecular-modulation technique applied to C12-H,029b and i.r. studies of the radical produced by photolysing 0,-H,O or 0,-HCl mixturesgc have yielded values for H-0 = 96 pm 0-0 = 130 pm," andLHOO = 105 5°.9b9c The nature of inorganic peroxides in general has been reviewed." The first volume of what promises to be an excellent four-volume treatise on water has appeared."" In a brief review on the distribution of electronic charge in the H,O molecule electronegativity ionization potentials electron affinities, 'all-atom' valence-bond resonance structures and the electronic charge distribu-tion on the 0 atoms in OF, Li,O and Cs,O have been discussed."b There has been controversy over the interpretation of near-infrared spectra of water-acetone solutions.'20~ It has been again suggested that the structure of the hydrogen-bonded water dimer in CC1 solutions is linearlZc and the symmetrical cyclic structure suggested earlier' 2 d v e represents a transition state for interconversion of the linear structure.Ab initio LCAO-MO-SCF calcula-tions performed on the pairs of mixed dimers NH,OH-H,O and HOF-H,O show that they have the equilibrium open-chain structure.' 2f Because of apparent inadequacies of the corrected liquid-drop model which, in addition to applying bulk properties to small clusters predicts nucleation rates that can be 10' times larger than experimental values a molecular model applic-able to prenucleation water clusters has been described and applied to water clusters with clathrate-like structures composed of five-membered rings.' 3a The water-cluster formation rates of NO + ' 3b and H 3 0 + ' 3c ions and the kinetics and G.E. Ewing Angew. Chem. Internat. Edn. 1972 11 486. (a) C. J. Hochanadel J. A. Ghormley and P. J. Ogren J. Chem. Phys. 1972,56,4426; ( b ) T.T. Paukert and H. S. Johnston ibid. p. 2824; (c) M. E. Jacox and D. E. Milligan, J . Mol. Spectroscopy 1972,42 495. ( a ) 'Water a Comprehensive Treatise Vol. 1 The Physics and Physical Chemistry of Water' ed. F. Franks Plenum Press New York 1972; (6) J. F. Liebman J . Chem. Educ. 1972,49 415. ( a ) A. Burneau and J. Corset J . Phys. Chem. 1972,76 449; (6) S. Subramanian and H. F. Fisher ibid. p. 452; ( c ) P. W. Atkins and M. C. R. Symons Mof. Phys. 1972, 23 831; ( d ) L. B. Magnusson J . Phys. Chem. 1970 74 4221; ( e ) L. B. Magnusson, Mol. Phys. 1971 21 571 ; (f) J. E. Del Bene J . Chem. Phys. 1972,57 1899. l 3 (a) P. L. M. Plummer and B. N . Hale J . Chem. Phys. 1972,56,4329; ( 6 ) C. J. Howard, H. W. Rundle and F. Kaufman ibid. 1971 55 4772; (c) C.E. Young and W. E. Falconer ibid. 1972 57 918; ( d ) C. J. Howard V. M. Bierbaum and H. W. Rundle, ibid. p. 3491. l o I. I. Vol'nov Uspekhi Khim. 1972 41 600 The Typical Elements 25 1 mechanism of the formation of water clusters from 02+ and H 2 0 have been studied.' 3d Novel approaches to water structure seem to have been made last year14a and current water structure models were reviewed in the latter half of the year.14b The most recent significant theoretical examination concludes that water is best described in terms of a continuum or interstitial model.'& The results of an attempt to estimate the extent of 'superstructuring' of liquid water on addition of non-electrolyte lead to the ordering and change in spectral properties of not less than 4000 molecules of water.' New data on the possibility of there being free OH groups in liquid water have shown that in spite of the complexity of the overtone regions of the spec-trum vibrational overtones do provide evidence of such groups.'6" Spectral features in the Raman spectra for water and its deuteriated analogues have been described in terms of vibrational stretching modes of two types of hydrogen-bonded water molecules the fully bonded four-co-ordinated species and the three-co-ordinated type which also has a free OH.16b The last few months of 1971 saw a spate of papers on anomalous water but few have appeared since.Reviews concentrated on the history of the pheno-menon.' 7od Theoreticians at first anxious to predict likely structures for 'polywater' are now explaining why it does not exist.'8u*b Therm~dynamic'~".~ and kinetic studies20 have confirmed that the phenomenon should be attributed to the condensation or adsorption of water on soluble impurities and ionic mobility studies have led to the conclusion that there are no significant structural anomalies in water near the solid boundaries in microcapillaries.2 ' These results have again been further supported by many observations of appreciable amounts of silica compounds,22"-S NaOH and NaC02H,23 or other organic contami-l 4 ( a ) D.W. A. Sharp M. G. H. Wallbridge and J. H. Holloway Ann. Reports 1971, 68 A 377; ( b ) I. Eliezer and P. Krindel Coordination Chem. Rev. 1971 6 217; (c) T. R. Chay and H. S. Frank J . Chem. Phys. 1972,57,2910. A. P. Zhukovskii and A.I. Sidorova Zhur. strukt. Khim. 1971 12 534. l 6 ( a ) J.-J. Peron C. Bourderon and C. Sandorfy Canad. J. Chem. 1971 49 3901; ( b ) W. F. Murphy and H. J. Bernstein J . Phys. Chem. 1972,76 1147. ' ( a ) L. C . Allen J. Colloid Interface Sci. 1971,36,554; (b) M . Herberhold Chem. Unserer Zeit 1971 5 154; ( c ) D. H . Everett Chem. Tech. (Amsterdam) 1971 26 311; ( d ) D. H. Everett J. M. Haynes and P. J. McElroy Sci. Progr. (London) 1971 235 279. ( a ) L. C. Allen and P. A. Kollman J. Colloid Interface Sci. 1971,36,469; ( 6 ) L. C. Allen and P. A. Kollman Nature 1971 233 550. l 9 (a) D. H. Everett J. M. Haynes and P. J. McElroy J . Colloid Interface Sci. 1971, 36 483; ( b ) D. H. Everett and P. J. McElroy ibid. p. 529. 'O E. H. Taylor J. Colloid Interface Sci.1971 36 543. J. L. Anderson and J. A. Quin J.C.S. Faraday I 1972,68 744. 2 2 ( a ) V. I. Spitsyn M. P. Glazunov V. M. Mulyar B. V. Deryagin N. V. Churaev and Z. M. Zorin Doklady Akad. Nauk S.S.S.R. 1972 202 132; ( b ) B. F. Howell and J. Lancaster J. Colloid Interface Sci. 1972,38,633; ( c ) M. P. Gingold Nature Phys. Sci., 1972 235 75; ( d ) M. Prigogine and J. J. Fripiat Bull. SOC. chim. France 1971 12, 4291; ( e ) M. Prigogine and J. J. Fripiat Chem. Phys. Letters 1971 12 107; ( f ) W. D. Bascom J . Phys. Chem. 1972,76,456. 23 S . Suzuki Vu Hai and B. Vodar J. Chim. phys. 1971,68 1385 252 D. W. A. Sharp M. G. H . Wallbridge and J. H. Holloway nant~.,~"' An X-ray diffraction study has provided evidence for a polycrystalline material obtained from an anomalous water sample but does not identify the material.25 Some workers,26avb notably Deryagin and Churaev,26a still maintain that anomalous water is a solution of a less volatile component 'Water II' in ordinary water.A crystal structure of picrylsulphonic acid tetrahydrate has shown that H 5 0 2 + ions water molecules and sulphonate groups are bonded together to form layers in the structure. The 0-0 distance in H,02+ is 242.9(2) pm.27a 1.r. and Raman studies of crystalline HC1,2H,O have also confirmed the occurrence of the H 5 0 2 + ion and fundamental vibrations have been assigned.," Hypofluorous acid HOF discovered last year has been the subject of n.m.r.'*O and i.r.28b,c investigations. The Raman spectrum of 04F2 was obtained by photolysing a 3 l(v/v) solution of OF in liquid oxygen at 90 K.29a No Raman evidence of 0,F radicals was found though e.s.r.signals due to the radical had been observed several years ago.29b Reactions of O,F and O,F with SO2 yield principally F,SO, with smaller amounts of F2S205 and FS0,OOF. The FS0,OOF results from an OOF intermediate and 04F2 provides the better source of OOF.29' Studies of the reaction H + OF * HFS + OF in the microwave cavity of an e.s.r. spectrometer have provided a value of 2.52 eV (243 kJ mol-') for the binding energy of OF.30a New mass spectrometric investigations of the OF radical30b,' have established a rate constant k = 1.7 x 1013 exp( -E/RT) cm3 mol- ' for the reaction3'' and a dissociation energy of Doo (0-F) = 2.2 eV (215 kJ mol-').30' Argon-matrix Raman spectra of OF and have confirmed earlier i.r.work and Raman and i.r. data for crystal-line OF indicate that the solid is not centrosymmetric and contains at least two molecules per primitive cell on sites of symmetry C or C,.31b A continuous 2 4 ( a ) S . B. Brummer J. I. Bradspies G. Entine C. Leung and H. Lingertat J . Phys. Chem. 1972,76,457; ( 6 ) R. J. Jakobsen U.S. Nat. Tech. Inform. Serv. AD Rep. 1972, No. 737309 [Gout. Rep. Announce. (U.S.) 1972 72 no. 7 p. 661; (c) D. L. Rousseau, J . Colloid Interface Sci. 1971 36 434; ( d ) E. R. Lippincott J. M. Casper and P. Schuhmann U.S. Nat. Tech. Inform. Serv. AD Rep. 1972 No. 739673 [Gout. Rep. Announce. (U.S.) 1972 72 no. 10 p. 691. 2 5 G. A. Petsko and W. R. Massey jun. J . Colloid Interface Sci. 1971 36 508. 2 6 ( a ) B.V. Deryagin and N. V. Churaev J . Colloid Interface Sci. 1971 36 415; ( 6 ) T. F. Page jun. and R. J. Jakobsen ibid. p.427. " ( a ) J . 0. Lundgren Acta Cryst. 1972 B28 1684; (6) J. Roziere and J. Potier J . Mol. Structure 1972 13 91. (a) J. C. Hindman A. Svirmickas and E. H. Appelman J . Chem. Phys. 1972 57, 4542; ( b ) E. H. Appelman and H. Kim ibid. p. 3272; (c) E. F. Pearson and H. Kim, ibid. p. 4230. 2 9 (a) D . J. Gardiner and J. J. Turner J . Fluorine Chem. 1972,1 373; (6) N. J. Lawrence, J. S. Ogden and J. J. Turner J . Chem. SOC. ( A ) 1968 3100; (c) I. J. Solomon and A. J. Kacmarek J . Fluorine Chem. 1971 1 255. 30 ( a ) D. H. Levy J . Chem. Phys. 1972 56 1415; (6) H. G . Wagner C. Zetsch and J. Warnatz Ber. Bunsengesellschaft phys. Chem. 1972 76 526; (c) M.A. A. Clyne and R. T. Watson Chem. Phys. Letters 1971 12 344. ( a ) L. Andrews J . Chem. Phys. 1972 57 5 1 ; ( 6 ) J. Tremblay and R. Savoie Canad. J . Chem. 1971,49 3785 The Typical Elements 253 preparation of OF from elemental fluorine and alkali-metal hydroxide in a spray-nozzle tube-reactor has been de~cribed.~ Several kinetic studies on OF reactions have been carried out. Pyrolysis gives rise to only 0 and F, and a radical chain mechanism has been proposed for the slightly-less-than-first-order reaction.33u The kinetics of the hydrolysis of dissolved OF (OF + 20H- + 0 + 2F- + H20),33b the reaction 20F + 3H --+ 4HF + H,O + 0.502,33" and the reaction of COF with OF in the presence of CsF'Ob have been studied. Irradiation of a gaseous mixture of OF and ClF in a quartz flask gives [C10F2]2[SiF6].34 The dissociation of this compound provides another route to the new compound ClOF (see Group VII).Sulphur .-Molecular orbital calculations on SO,'- 35a4 SO ,35d*e S0,F2, S0,Cl,,35c H2S,3se,J H2S02,35J CS2,35e and SF635g have furthered the debate concerning d-orbital participation in the bonding. The involvement of 3d orbitals in the bonding of dialkyl sulphoxides (R2SO)36a and dialkyl sulphones (R,S0,),36b and their derivatives has also been discussed. Quadrupole moments calculated by the CNDO method for Me,& SO, thiophen and SO,F agree better with experimental values when 3d orbital polarization functions are included.37 Neutral S (x = 2 4 ) S,- S3- and S,- have all been proposed as species which might account for the blue colour which develops when sulphur is heated with water in the presence of a basic salt or when sulphur is dissolved in molten alkali metals or alkali-metal polysulphides in basic solvents.New spectroscopic, conductivity and magnetic susceptibility measurements suggest that the species is in fact the S3- radical anion.38 New studies have shown that the configuration of the SS2+ cation is that of a folded ring,39" similar to that of the SeS2+ ion reported earlier.39b Absorption 32 K. H. Hellberg and J. Massonne Ger. Offen. 2 026 9 17/ 197 1 . 3 3 (a) T. J. Houser and T. W. Asmus J. Amer. Chem. Soc. 1972,94,3326; ( 6 ) S. N. Misra and G. H. Cady Inorg. Chem. 1972 11 1132; (c) T. W. Asmus and T. J. Houser, ibid. p. 234. 3 4 K. Zuchner and 0.Glemser Angew. Chem. Internat. Edn. 1972 11 1094. 3 5 (a) U. Gelius B. Roos and P. Siegbahn Theor. Chim. Acta 1971 23 59; ( 6 ) K. H. Johnson and F. C. Smith Internat. J . Quantum Chem. Symp. 1971 5. 429; (c) M. F. Guest and I. H. Hillier Internat. J. Quantum Chem. 1972,6,967; see also R. L. DeKock, D. R. Lloyd I. H. Hillier and V. R. Saunders Proc. Roy. Soc. 1972 A328 401; ( d ) M. F. Guest I. H. Hillier and V. R. Saunders J.C.S. Faraday 11 1972 68 114; ( e ) M. S. Nakhmanson V. I . Baranovskii and A. I. Panin Vestnik Leningrad. Uniu. (Fiz. Khim.) 1972 2 35; (f) J. R. Van Wazer and I. Absar Adv. Chem. Ser. 1972 110, 20; ( g ) F. A. Gianturco C. Guidotti U. Lamanna and R. Moccia Chem. Phys. Letters, 197 1 10 269. 3 6 ( a ) H. Bock and B. Solouki Angew.Chem. Internat. Edn. 1972,11,436; ( 6 ) B. Solouki, H. Bock and R. Appel ibid. p. 927. 3' H. L. Hase and A. Schweig Chem. Phys. Letters 1971 12 238. 3 8 T. Chivers and I. Drummond Inorg. Chem. 1972 11 2525. 39 (a) C. G. Davies R. J. Gillespie J. J. Park and J. Passmore Inorg. Chem. 1971 10, 2781; ( b ) R. K. McMullan D. J. Prince and J. D. Corbett ibid. p. 1749; ( c ) R. J. Gillespie and P. K. Ummat ibid. 1972 11 167; ( d ) R. A. Beaudet and P. J. Stephens, Chem. Comm. 1971,1083; ( e ) M. C. R. Symons and J. G. Wilkinson Nature Phys. Sci., 1972 236 126; (f) M. Herlem A. Thiebault and G. Adhami Analyt Letters 1972, 5 309 254 D. W. A . Sharp M . 6. H. Wallbridge and J . H . Holloway and e.s.r. spectra together with cryoscopic measurements have shown that solutions of sulphur in oleum are successively oxidized to S162+ Sg2+ s42+, and SO with time or increasing SO concentration.It appears from e.s.r. data that equilibria exist between Slb2+ and s8+ and between Ss2+ and S42+.39c Independent e.s.r. work supports an earlier proposal39d that the paramagnetic cation in solutions of oleum is S,+ formed by the oxidation of S8.,'= The ions S2+ S+ S2+ and S4+ have been observed in HS0,F-sulphur mixtures.39f The cation SA2 + is included in a general theory for clusters and ring compounds in which rules for explaining and predicting the geometries of electron-precise or -rich polynuclear aggregates on the basis of the number of skeletal electron pairs have been o~tlined.~' The existence of S and S in sulphur vapour at intermediate temperature and pressure has been recognized for several years.Assignment of the visible spectra of the two species has now been made and the characteristic absorptions found in hot liquid sulphur and trapped liquid ~ulphur.~' The polyatomic sulphur-chain compound diethyl 1,1-(cycloheptasulphanyl)hydrazine-2,2-dicarboxylate (57) has been prepared by the reaction of S7C12 with H,NN(CO,Et) in Et20 in the presence of Et3N.42a An X-ray structure determination of the third isomer of S6(NH) has shown that it is cyclohexasulphur-l,3-di-imide (58) rather than cyclohexasulphur-1,2-di-imide.42b Heptasulphur imide S7NH reacts with di-borane in an analogous way to reactions with BCl and BBr to give S,NBH .42c Cyclo-octasulphur oxide S 8 0 (59 ; n = 7) has been synthesized by means of the \ \ / NN(C0 Et)2 /s-s-s S s-s-s-(57) (58) The pseudo mirror plane of the molecule is given by m C1 H / \ \ / O=S + S -+ S + 1 0 + 2HC1 C1 H (59) 40 D.M. P. Mingos Nature Phys. Sci. 1972 236 99. 4 1 B. Meyer T. Stroyer-Hansen and T. V. Oommen J . MoI. Spectroscopy 1972,42,335. 4 2 ( a ) K. H. Linke and D. Skupin 2. Nuturforsch 1971 26b 1371; (b) H. J. Postma, F. Van Bolvil and A! Vos Acta Cryst. 1971 B27 2480; ( c ) M. H. Mendelsohn and W. L. Jolly Inorg. Chem. 1972 11 1944; (d) R. Steudel and M. Rebsch Angew. Chem. Internat. Edn. 1972 11 302; (e) H. G. Heal M. S. Shahid and H. Garcia-Fernandez J. Chem. SOC. ( A ) 1971 3846 The Typical Elements 255 well-known ring-closure reaction using crude sulphane. This is the first compound of the class which can be obtained in the pure state and the structure is probably that of a zig-zag S ring with an equatorial or axial 0 atom.42d Attempts to make S,N2 (60) and S13N2 (61) by coupling 1,3-hexasulphur di-imide with S S s-s / \ / \ / \ S N-S S N S I S I I I I I s s s s s I S I I I I I S N S N-S \ / \ / \ / S S s-s (60) (61) S3C12 or S,Cl respectively have failed.42' Pseudo single crystals of (SN) are obtained by the polymerization of S,N2 at liquid-nitrogen temperature., The first oxide of the S4N4 ring (62) has recently been isolated from the reaction of NN'-bis(trimethy1silyl)sulphur di-imide with the anhydride of fluorosulphuric acid.44a Tetrathiazyl tetra[bis(trifluoromethyl) 2 Me,Si-N=S=N-SiMe + 2 FS0,-0-S0,F + O N N O 0 / \ N N \ / \ / \ / S S + 2 Me,SiF + 2 Me,SiOSO,F NS/ (62) nitroxide] N,S,[ON(CF,),], has been prepared by the reaction of S,N4, N4S4H4 or N,S,Cl with liquid (CF,),NO*.The same white crystalline solid can also be obtained by the reaction of N3S,C1 with Hg[ON(CF,),] .44b The reaction of S,N4 with SOC1 in the presence of iron(u1) or aluminium chloride has yielded mixtures of tetrachlorometallates of the cations S,N,Cl+ S,N + , and S5N5+.44c The salts S5N5+A- (A = AlCI, FeCl, or SbCI,) can also be readily prepared in high yield from S4N4 (NSCl), and the metal Simple 1 1 adducts of S4N with aluminium chloride or bromide have also been obtained and the reaction of the AlCI adduct with SbC1 has been described.,,' Sulphur-nitrogen-halogen compounds have been briefly reviewed45a and methods of preparation properties and derivatives of some sulphanuric com-4 3 M.Boudeulle A. Douillard P. Michel and G. Vallet Comp. rend 1971 272 C 2137. *' ( a ) H. W. Roesky and 0. Petersen Angew. Chem. Internat. Edn. 1972 11 918; (b) H. J. Emeltus and R. J. Poulet J. Fluorine Chem. 1971 1 1 3 ; (c) A. J. Banister and P. J. Dainty J . C.S. Dalton 1972,2658; ( d ) A. J. Banister and P. J. Dainty ibid. p. 2661 ; (e) C. H. Chan and F. P. Olsen Znorg. Chem. 1972 11 2836 256 D. W. A . Sharp M . G. H. Wallbridge and J. H. Holloway pounds have been described.45b Heats of fusion and decomposition have been obtained for (SNOX) and S,N,O,XPh (X = F or C1) using a differential scanning calorimeter.45c An X-ray crystal-structure determination on N,S,F has shown a six-membered ring of alternating S and N atoms with a chair conformation.All the S-N bond lengths are equal through delocalized d,-p bonds in keeping with other halogeno- and oxohalogeno-cyclothiazenes.46 Microwave examination of NSCl has provided force constants and a value for the dipole moment.47" It has been shown that the action of SO,Cl (rather than Cl,) on S4N4 or S3N2Cl+C1-provides a better route to the formation of (NSCl) .47b Derivatives of thiotrithiazyl chloride of the types S,N,X and S,N,O,SMe,-H0,SMe have been obtained by the reaction of S4N3Cl with HX [X = O,SMe, O,SCF N(SO,F) N(SO,CF,)SO,Cl or N(S02CF3)S02F].47C A new poly-mer S,,N,CI, has been claimed to result from the thermal reaction between sulphur and nitrogen in the presence of urea.47d Reviews on binary and ternary sulphur-containing systems including S-0, S-SO S-H,S S-Se and S-I,48" and little-known and non-commercial uses of SO ,48b have been published.Phase equilibrium studies on the SO,-quinol clathrate indicate that aqueous quinol solutions may be of value as SO absor-b a n t ~ . ~ ~ Ab initio MO-SCF-LCAO calculations have been performed on SO,, SO,- and SO,,- in an attempt to provide information about the electronic changes which occur when SO co-ordinates to transition-metal and the first complex in which SO alone bridges two metal atoms has been synthesized and unambiguously characterized as (63) by X-ray diffraction. The material was separated chromatographically from the products of reaction of SO with .n-C,H,Fe(CO),Na in tetrahydr~furan.,'~ An electron-diffraction investigation on SO is not in perfect agreement with the results from earlier spectroscopic work possibly on account of traces of S,O in the diffracting ~ a p o u r .~ ' Complexes of SO with acetyl and mono-chloroacetyl chlorides nitrosyl and nitryl chlorides phosphoryl chloride seleninyl 4 5 ( a ) 0. M. Glemser Internat. J. Sulfur Chem. (C) 1971 6 35; (b) T. Moeller and R. L. Dieck in 'Preparative Inorganic Reactions' ed. W. L. Jolly Wiley-Interscience New York 1971 vol. 6; (c) R. L. McKenney and N. R. Fetter J. Inorg. Nuclear Chem. 1972, 34 3569. 4 6 B. Krebs S. Pohl and 0. Glemser J.C.S. Chem. Comm. 1972 548. 4 7 (a) S. Mizumoto J. Izumi T. Beppu and E. Hirota Bull. Chem. Sac. Japan 1972, 45 786; (b) G.B. Alange A. J. Banister and B. Bell J.C.S. Dalton 1972 2399; ( c ) H. W. Roesky and M. Dietl Z . Naturforsch. 1971 26b 977; ( d ) S. Rajeswari Indian J . Chem. 1972 10 441. 4 8 ( a ) T. K. Wiewiorowski in 'MTP Internat. Rev. Sci. Inorg. Chem. Ser. One' 1972, 2 171 ed. C. C. Addison Butterworths London 1972; ( 6 ) R. Leclercq D. W. Bixby, and H. L. Fike Sulphur Inst. Tech. Buff. 1972 no. 19. 4 9 Y. Yokoyama and G. Konno Kagaku Kogaku 1972,36,629. '" (a) P. D. Dacre and M. Elder Theor. Chim. Acta 1972 25 254; (b) M. R. Churchill, B. G. Deboer K. L. Kalra P. Reich-Rohrwig and A. Wojcicki J.C.S. Chem. Comm., 1972,98 1 . 5 1 A. H. Clark and B. Beagley Trans. Faraday Soc. 1971,67,2216 The Typical Elements 257 chloride,52” and oxides of nitrogen52b have been prepared.Spectroscopic studies indicate that only the ClCH,COCl and SeOCl adducts are n o n - i ~ n i c . ~ ~ ” The rest contain anions such as S 2 0 7 2 - S3OIo2- and s401,~-. Reactions of SO, with K$407 and KB,O have given B2O,,SO, K2B402(S04) (64) and K2B,0(S04) .52c The chemistry of the fluorinated p-sultones (65) formed by K2 r 0 0 B- y \ /O\ B / \ / I I 0 0 0 0 0 II II 0 .o-s-the addition of SO to polyfluoro-olefins has been reviewed.52d New thermo-dynamic functions for a variety of oxygenated sulphur complex ions have been obtained from heat capacity and heat of solution measurement^.^^ The crystal structures of H2S04,4H,0 and its deuteriated analogue have shown that the structure consists of H502+ (cf. ref. 27b) and Sod2- ions hydrogen-5 2 ( a ) R.C . Paul C. L. Arora and K. C. Malhotra Zndian.J. Chem. 1972 10 92; (b) R. C. Paul C. L. Arora and K. C. Malhotra ibid. p. 94; (c.) S. N. Kondrat’ev and S. I. Mel’nikova Zhur. neorg. Khim. 1972 17 940; ( d ) I. L. Knunyants and G. A. Sokolski Angew. Chem. Internat. Edn. 1972,11 583. 5 3 J . W. Cobble H. P. Stephens I. R. McKinnon and E. F. Westrum jun. Znorg. Chem., 1972 1 1 1669 258 D. W. A . Sharp M . G . H. Wallbridge and J. H. Holloway bonded to each other in a three-dimensional network. All the S - 0 bonds in the SO,'- ion are eq~ivalent.~," Attempts have also been made to gain informa-tion on the liquid structure of 100% H2S04 from X-ray d i f f r a ~ t i o n ~ ~ ~ ~ ' and equilibrium compositions in sulphuric acid solutions have been studied by i.r.and Raman method^.^,^.^ Reactions in fluorosulphuric acid have continued to provoke interest. The reactions of some metal chlorides and organic and inorganic bases5'" and redox reactions with Br, Cl, IC1 and NOCl as oxidizing agents and P"' and As"' as reducing agents5 5b have been examined conductimetrically. Nitronium and nitrosyl fluorosulphates have been isolated from the reactions of oxides of nitrogen with fluorosulphuric acid and P z 0 5 forms a mixture of disulphuryl and tri-sulphuryl fluorides. Oxides of As Sb and Bi form fluorosulphates and SO gives pyrofluorosulphuric acid.5 5' However the earlier work which purported to have identified yellow Sb4,+ and blue Sbs2+ ionsssd has not been substantiated by recent work which clearly shows that colourless SbS0,F is formed and that the blueand yellowcoloursaredue to thereductionofthesolvent t ~ s u l p h u r c a t i o n s .~ ~ ~ Ionization energies and electron affinities have been calculated for SF SF,, SF, and SF in a molecular-orbital study of their binding energie~.~" Investiga-tions of ion-molecule reactions of S,F in the gas phase have shown sulphur-transfer reactions to dominate over fluorine-transfer reaction^.^ ' Raman and i.r. spectra of solid SF have revealed three distinct forms during annealing from liquid-nitrogen temperature.58a Pure F,SSF has been prepared by the reaction of SCl with KF in glass which has been conditioned with SF, and the stretching vibrations of the SF and SF groups have been assigned.58b Those of SF,', previously determined from the spectra of solids have been confirmed by Raman spectroscopic polarization measurements on solutions of SF +BF4- SF +PF6-, and SF,+AsF,- in anhydrous HF.58f A new radical S,Cl has been observed for the first time by e m .methods.59 The reaction of S2C1 with hydrazine in a 5 2 molar ratio in diethyl ether resulted in the oxidation of N2H4 to nitrogen and the reduction of S,Cl to sulphur. 5 4 (a) T. Kjallman and I. Olovsson Acta Crysr. 1972 B28 1692; (b) J. U. Weidner H. Geisenfelder and H. Zimmermann Ber. Bunsengesellschaftphys. Chem. 197 1,75,800; (c) J. U. Weidner H. Geisenfelder and H. Zimmermann ibid. 1972 76 628; (d) N. B. Librovich and V. D. Maiorov Doklady Akad. Nauk S.S.S.R. 1971 198 1371; ( e ) N. G. Zarakhani N. B. Librovich and M.I. Vinnik Zhur. fiz. Khim. 1971 45, 1733. 5 5 (a) R. C. Paul K. K. Paul and K. C. Malhotra J . Inorg. Nuclear Chem. 1972 34, 2523; (6) R. C. Paul S. K. Sharma K. K. Paul and K. C. Malhotra ibid. p. 2535; (c) R. C. Paul S. K. Sharma R. D. Sharma K. K. Paul and K. C. Malhotra ibid., 1971,33,2905; (d) R . C. Paul K. K. Paul and K. C. Malhotra Chem. Comm. 1970, 453; ( e ) R. J. Gillespie and 0. C. Vaidya J.C.S. Chem. Comm. 1972 40. 5 6 A. L. Companion Theor. Chim. Acta 1972,25,268. 5 7 K. P. Wanczek K. H. Lebert and H. Hartman 2. Naturforsch. 1972 27a 155. 5 8 ( a ) C. V. Berney J. Mol. Structure 1972 12 87; (6) F. See1 and R. Budenz J. Fluorine Chem. 1971 1 117; (c) M. Brownstein and J. Shamir Appl. Spectroscopy 1972 26, 77. 5 9 F. G. Herring C. A. McDowell and J.C. Tait J. Chem. Phys. 1972 57 4564 The Typical Elements 259 However the 1 1 reaction with MeNHNHMe produced a cyclic dihydrazide (66).60a With LiN=C(CF,) disulphur dichloride produced bis(hexafluoroiso-propylidenimino) disulphide [(CF,),C=N],S, which reacts further in two s-s / \ MeN NMe I I MeN s-s (66) \ /NMe different ways with C1 to give (CF,),CClN=S=NCCl(CF,) and (CF,),C= NSCl. This latter compound is readily attacked by compounds such as dimethyl-amine and NH to give substituted sulphenyl compounds by cleavage of the S-Cl bond.60b The reaction of SCl with Me,SiN=S=O in a nitrogen atmo-sphere has provided a new route to S(NSO) . The second product of the reaction, Me,SiCl proved to be an excellent solvent for S(NSO) .60c An attempt to assess the extent that MO calculations in conjunction with an approximate force field can be useful in confirming a set of vibrational assign-ments has been made using Raman data for SF,.61 Reaction of SF4 with LiN=C(CF,) (cf ref.60b) has resulted in the formation of five new compounds each of which arises indirectly from the reaction of the lithium salt on the sulphur difluoride imide.62a This contrasts with the predict-able metathesis reactions observed with other inorganic chlorides and fluorides.62b Although it is well known that Si(NCO) reacts slowly with SF to produce F2S=NC(0)F in good yield it has only recently been shown that if excess of Si(NCO) is used the reaction goes further to produce F,S=NC(0)NC0.62C Fluorine-18 exchange reactions between SF and Group I fluorides have been discussed in relation to the formation of SF,- as intermediate.63" Vibrational spectra of the CsF adducts of SF (and SeF,) indicate a close resemblance with those of the isoelectronic molecules ClF and BrF .This is indicative of square-pyramidal anions of C4" symmetry63b and is in close agreement with independent results published last year.63c Ionization energies of SF calculated by the multiple scattering method are in better agreement with recent X-ray photoelectron spectroscopic data than either ( a ) H. Lingmann and K. H. Linke 2. Naturforsch. 1971 26b 1207; (b) S. G. Metcalf and J. M. Shreeve Inorg. Chem. 1972,11 1631 ; (c) D. A. Armitage and A. W. Sinden, ibid. p. 1 1 5 1 . I. W. Levin J . Chem. Phys. 1971 55 5393. (a) R.F. Swindell and J. M. Shreeve J . Amer. Chem. SOC. 1972 94 5713; (6) R. F. Swindell D. P. Babb T. J. Ouellette and J. M. Shreeve Inorg. Chem. 1972 11 242; ( c ) A. F. Clifford J. S. Harman and C. A. McAuliffe Inorg. Nuclear Chem. Letters, 1972 8 567. ( a ) C. J. W. Fraser D. W. A. Sharp G. Webb and J. M. Winfield J.C.S. Dalton, 1972 2226; (b) K. 0. Christe E. C. Curtis C. J. Schack and D. Pilipovich Inorg. Chem. 1972,11 1679; ( c ) L. F. Drullinger and J. E. Griffiths Spectrochim. Acta 1971, 27A 1793 260 D. W. A . Sharp M . G. H . Wallbridge and J . H . Holloway ab initio (SCF-MO-LCAO) or semi-empirical (CNDO) results.64 Mass spectro-metric examination of POF,-SF and PSF3-SF6 mixtures has shown that the principal ion-molecule reaction involves the reaction of SF - with POF and PSF to give POF,- and PSF4- re~pectively.~ A patent on the preparation of SF,Cl by the interaction of ClF and SF in the presence of CsF in a Monel cylinder has appeared,66" and inferences about the chemical bonds in the molecule have been drawn from a stud; of the quadrupole hyperfine effects in the micro-wave spectrum.66b An electron-diffraction study of SF,NF gas has provided values for bond distances and angles in the Vibrational analyses of SOF SOCI ,67a SOBr 6 7 0 3 SO,F, S02C12,67c SO,FCI and S0,FBr67"-e have been carried out and the rotational spectra of S035C137C1 has been studied between 8000 and 80000 M H z .~ ~ ~ A microwave study of S0,CIF has provided new values for bond lengths and angles.68 An unusual structure with novel bonding has been proposed for S02C1 - from e.s.r.measurements. The structure is visualized as a radical-anion complex of SO and C1 in which the unpaired electron is associated with the lowest un-occupied orbitals of both molecule^.^^ 17+S03F- and a variety of previously known iodine species have been detected in the iodine-peroxydisulphuryl difluoride system.70a Oxyfluoro-sulphates of several and CeF,(S0,F)70b have been obtained in reactions of peroxydisulphuryl difluoride with the metal carbonates or oxides and CeF, respectively. The new compounds PCl,+SO,F- PC1,BrfSO,F-, PPh3C1+S03F- and PPh,Br+SO,F- have been isolated from fluorosulphuric acid High-purity SOF has been prepared almost quantitatively by the reaction of SOF with BrF ;it was also prepared from SOF and ClF .'la Monosubstituted derivatives of thionyl tetrafluoride have been obtained from the reaction between silylamines and SOF on many occasions and now it has been shown that silyl ethers also produce substitution and that in some cases 2 3 or 4 fluorines can be replaced.71b Reactions of OSF4 with AN(SiMe,) [A = Li or Na] in 1 1 and 1 2 molar ratios has given OSF,NSiMe and OS( NSiMe,) re~pectively.~ Electronic i.r.and Raman spectroscopy has been used to study XS0,- ions in halide-ion-SO mixtures. The vibrational spectra are consistent with the b4 J. W. D. Connolly and K. H. Johnson Chem. Phys. Letters 1971 10 616. 65 T. C. Rhyne and J . G. Dillard Internat. J . Mass Spectrometry Ion Phys. 1971,7 371. 6 6 ( a ) C. J . Schack and R. D. Wilson U.S.P. 3649222/1972; ( 6 ) K.S. R. Murty and A. K. Mohanty Indian J . Phys. 1971-72 44 635; ( c ) J. Haase H. Oberhammer, W. Zeil 0. Glemser and R. Mews Z . Naturforsch. 1971 26a 1333. 6 7 ( a ) R. A. Suthers and T. Henshall Z . anorg. Chem. 1972,388,269; (6) K. Ramaswamy and S. Jayaraman Indian J . Pure Appl. Phys. 1972 10 72; (c) R. A. Suthers and T. Henshall Z . anorg. Chem. 1972,388,257; (d) B. N. Cyvin and S. J. Cyvin Acra Chem. Scand. 1972 26 1284; ( e ) K. Ramaswamy and S. Jayaraman J . Mol. Structure 1971, 10 183; (f) A. Dubrulle and D. Boucher Compt. rend. 1972 274 B 1426. '* C. W. Holt and M. C. L. Gerry Chem. Phys. Letters 1971,9 621. 6 9 C. M. Kerr and F. Williams J . Amer. Chem. Soc. 1972 94 5212. 'O ( a ) C. Chungand G. H. Cady Inorg. Chem. 1972,11,2528; ( 6 ) R.Dev W. M. Johnson, and G. H. Cady ibid. p. 2259; (c) R. Dev and G. H. Cady ibid. 1971 10 2354. 7 1 ( a ) K. Seppelt Z . anorg. Chem. 1971 386 229; ( 6 ) D. S. Ross and D. W. A. Sharp, J.C.S. Dalton 1972 34; ( c ) 0. Glemser M. Feser S. P. Von Halasz and H. Saran, Inorg. Nuclear Chem. Letters 1972 8 321 The Typical Elements 26 1 expected (C,) geometry and it appears that the magnitude of the X-SO inter-action is in the order FS0,- > ClS0,- < BrS0,- < ISO,-?, Infrared and Raman spectra of Me,S Me,SO and Me,SO and their per-deuteriated analogues have been studied and their normal vibrations assigned.73 Calorimetric studies of water-dimethyl sulphoxide adducts in dioxan and enthalpies of transfer of halide ions in aqueous Me,SO have been made. A temperature-dependent equilibrium between Me2S0,2H,O and Me2S0,3H,0 has been proposed to correlate literature data on the Me,SO-H,O s ys tem.4c The first four-co-ordinated sulphur(1v) compound without halogen atom ligands Ph,S[OC(CF,),Ph] has recently been reported75" and an X-ray study has shown that the alkoxy-ligands occupy the apical positions of a trigonal bipyramid in the as was suggested by 19F n.m.r. data for the molecule in s ~ l u t i o n . ~ 5a The magnetic non-equivalence of the diastereotopic groups in alkylsulphinyl chlorides76"* and some new chlorosulphites76a has been demonstrated. The structure of diphenyl disulphone PhS(O)S(O)Ph has provided yet another example of a long S-S bond. Discussion of the theoretical implications suggests that the unusual length of these bonds in disulphides and oxy-disulphides have not been satisfactorily e~plained.~ Additionofnucleophilicreagents to sulphenes(R'R2C=S0,) has been regarded for some time as one of the most important reactions of these reactive inter-mediates.In an examination of reactions of sulphenes with tervalent phosphorus compounds PhCH,SO,X [X = C1 or OC,H,(N02),-o,p] reacted with a Ph,P-Et,N mixture to give PhCH,P+Ph,X- in each case. The mechanism PhCH-SO, can be explained in terms of a cyclic intermediate the zwitterions PhCH-CO,$Ph or PhCH-S02-.78a \ / or perhaps via PPh, / Sulphene-tertiary amine zwitterions (CHR1S0,kR2,) have been suggested as intermediates in the multi-exchange of hydrogen in the formation of sulphenes by the action of bases on alkanesulphonyl ~hlorides.~~' l 2 D.F. Burow Inorg. Chem. 1972,11 573. l 3 G . Geiseler and G. Hanschmann J . Mof. Structure 1972 11 283. l 4 ( a ) F. Rallo and F. Rodante Ann. Chim. (Italy) 1972 62 221 ; ( b ) R. Fuchs D. S. Plumlee,jun. and R. F. Rodewald Thermochim. Acto 1971 2 515; ( c ) E. A. Symons, Canad. J . Chem. 1971,49,3940. 75 ( a ) J. C. Martin and R. J. Arhart J . Amer. Chem. SOC. 1971 93 2341; ( 6 ) I. C. Paul, J. C. Martin and E. F. Perozzi ibid. p. 6674. l 6 ( a ) M. Mikolajczyk and J. Drabowicz 2. Naturforsch. 1971,26b 1372; ( b ) G. Canalini, G. Maccagnani and F. Taddei Tetrahedron Letters 1971 3035. l 7 C. Th. Kiers and A. Vos Rec. Trav. chim. 1972 91 126. '* ( a ) J. F. King E. G. Lewars and L. J. Danks Canad. J . Chem. 1972 50 866; ( 6 ) J.F. King E. A. Luinstra and D. R. K. Harding J . C . S . Chem. Comm. 1972 1313 262 D. W. A . Sharp M. G. H. Wallbridge and J. H. Holloway 0 moiety has received attention during the past few years. For example it is known that polymers containing the group are formed when SOF reacts with ammonia. The anal-ogous reaction using bis(perfluoroalky1)sulphur oxydifluorides has now been examined and the first bis(perfluoroalky1)sulphur oxyimines (CF,),S(O)NH, CF,(C,F,)S(O)NH and (C,F,),S(O)NH have been prepared and some of their chemistry in~estigated.~~ The thermal transformations of sulphuryl di-imide, SO,(NH), between 370 and 470 K have given rise to a variety of compounds, including cyclic (NH,NSO,) ; there is evidence that the ring forms via linear oligomers." The similarity between O=SF and R,N=SF (R = perhalogenoalkyl) has been borne out by a study of the reactions of the -N=SF group in sulphur difluoride N-perhalogenoalkylimides which are readily exchanged by R' ,NSiMe,, R1N(SiMe2), or R'ONa to give compounds of general formula R,N=S(NR',)F, R,N=S(NR',), RxN=S=N-R' RxN=S(OR')F and R,N=S(OR') .81 Selenium and Tellurium.-A translation of a Russian book on selenium and the selenides*," and a review of the chemistry of inorganic selenium have appeared recently.The X-ray crystallographic determination of the structure of Se,(HS,O,), has shown that the Se,' + cation is ~quare-planar~~ and Te,(AlCI,) and Te,-(Al2Cl,) have been shown to contain Te4,+ which is like Se42+.84a In both cases the M-M bond distance in the cation is shorter than the M-M single-bond distance indicating a bond order greater than unity.Claims that yellow compounds containing tellurium in the + 1 oxidation state are Te," species have been Selenium and tellurium chains have also been the subject of a number of publications during the past twelve months. Two types of extended-chain crystals have been obtained by quenching pure liquid Se in evacuated Pyrex ~apillaries.~~" The selenopentathionate ion (which contains the S-S-Se-S-S \ / / \ The chemistry of compounds containing the S N-79 D. T. Sauer and J. M. Shreeve Inorg. Chem. 1972,11 238. Y. Ito Nippon Kagaku Kaishi 1972 320. R. Mews and 0. Glemser Znorg. Chem. 1972 11 2521. 8 2 ( a ) D. M. Chizhikov and V. P. Shchastlivyi 'Selenium and the Selenides' Gleichenhaus, New York 1971 ; ( 6 ) J.W. George in 'MTP Internat. Rev. Sci. Inorg. Chem. Ser. One' 1972 2 229 ed. C. C. Addison Butterworths London 1972. 83 I. D. Brown D. B. Crump and R. J. Gillespie inorg. Chem. 1971 10 2349. 84 (a) T. W. Couch D. A. Lokken and J. D. Corbett Inorg. Chern. 1972 11 357; (b) N. J. Bjerrum ibid. p. 2648; ( c ) R. C. Paul C. L. Arora J. K. Puri R. N. Virmani, and K. C. Malhotra J.C.S. Dalton 1972 781. .s5 ( a ) M. C. Coughlin and B. Wunderlich J . Polymer Sci. Part B Polymer Letters 1972, 10 57; (b) K. Boeyum and K. Maroey Acta Chem. Scand. 1971 25 2569; (c) A. Hordvik and K. Julshamn ibid. p. 2507; ( d ) G. Llabres 0. Dideberg and L. Dupont, ibid. 1972 28 2438; ( e ) C. J. Marsden and G. M. Sheldrick J . Mol. Strucrure 1971, 10 419; (f) W.Siebert and A. Ospici Chem. Ber. 1972 105 464 The Typical Elements 263 chain) has been observed for the first time in the transform in (NH,),Se(S,O,),-jH,0.85b The structure of 6a-selenaselenophthen (67) which contains a linear three-selenium-atom sequence built into an aromatic ring system has been 0 Se- Se- Se studied to find out to what extent the Se-Se bonds are shortened by n-b~nding.~" Diphenyl ditelluride PhTeTePh,85d and bis(trifluoromethy1) diselenide F3C-SeSeCF ,85e structures have been determined by X-ray analysis and electron diffraction respectively. An unusual ring compound (PhB),Se (68) has resulted Se-Se / \ Ph-B B-Ph (68) from a rearrangement reaction of the phenylselenadi-iodoborane C,H,SeBI .8 sf Brief notes on the i.r.spectra and thermodynamic functions of Se0286a and Te0,86b have appeared and matrix Raman data for monomeric SeO have been reported for the first time.86c Polymerization of the latter in the matrix produced the dimer which was shown to have the centrosymmetric chair (C,,,) configuration, as well as higher aggregates.86' X-Ray single-crystal analysis of Te205 has shown that the structure is composed of [TeV'0,]n2"- sheets containing octahedral Te between which lie [Te'V0]n2n+ chains running parallel to the b-axis. The terminal oxygens in the TeV' octahedra are also bonded to the Te" forming a three-dimensional system.8 Electron-diffraction studies on the molecular structures of (F,C),Se88" and F3CSeCN88b have been carried out and the crystal structures of six Te" com-plexes e.g.tetrakis(selenourea)tellurium(II) and trans-diselenocyanatobis(tri-methylenethiourea)tellurium(r~),~ have been determined. Differential thermal analysis studies of SeO in dry nitrogen or oxygen atmo-spheres indicate that it decomposes in two stages to form Se205 as an inter-mediate.g0 Complexes of SeO of a 1 1 molar ratio have been prepared with 8 6 8 7 8 8 8 9 90 ( a ) S. Nunziante Cesaro M. Spoliti A. J. Hinchcliffe and J. S. Ogden J . Chem. Phys., 197 1,55,5834; ( b ) M. Spoliti S. Nunziante Cesaro and E. Coffari J . Chem. Therrnodyn., 1972,4 507; (c) G. A. Ozin and A. Vander Voet J . Mol. Structure 1971 10 173. 0. Lindqvist and J. Moret Acta Chem. Scand. 1972 26 829. ( a ) C. J. Marsden and G . M. Sheldrick J . Mol. Structure 1971 10 405; ( 6 ) C.J. Marsden and G. M. Sheldrick ibid. p. 413. See K. Ase 0. Foss and I. Roti Acta Chem. Scand. 1971 25 3808 and references therein. E. E. Sidorova S. N. Kondrat'ev K. N. Mochalov G. 1. Blagoveshchenskaya and K. P. Pribylov Zhur. neorg. Khim. 1972 17 299 264 D. W. A . Sharp M. G. H. Wallbridge and J. H. Holloway AsC1 SbCl, and SbCl in cold SO solutiong1o and with several organic tertiary bases in SO or MeN0,.91b These latter complexes are said to retain the SeO, tetrameric ring but the spectra of the 1 1 adducts with trimethylamine and pyridine prepared by the decomposition of the bis(trimethylsily1) selenate adducts have been assigned on the basis of monomeric molec~les.~'~ Despite several earlier attempts the structure of tellurium tetrachloride has only recently been shown by X-ray methods to be based on the tetrameric unit Te,Cl, with a co-ordination number of six for each Te atom.92" Other struc-tural investigations of interest include the covalent (Q) form of di-iodo(dimethy1)-tellurium which comprises three crystallographically independent Me,TeI, molecules in the asymmetric unit.In each molecule the tellurium has a distorted octahedral environment formed by two trans-Te-I bonds two cis-Te-C bonds, and two weak intermolecular Te - I contacts.92b The product of the reaction of TeBr and cyclohexane which was known to have the formula (TeBrC,H ,,), , has been shown to consist of molecules of Te2Br,C6Hl (69).92c An X-ray n (69) investigation of K,TeI has shown that the crystals are monoclinic rather than triclinic as was reported earlier and that the structure is more distorted than K,TeBr from the cubic K,PtCl structure.92d New spectroscopic data for SeF (Raman of solid liquid and gas and i.r.of gas) and SeOF (Raman of solid liquid and gas) have been reported and dis-cussed with special reference to polymerization in the condensed phases.93P 9 1 ( a ) J . Touzin and M. Jaros Z . Chem. 1971,11,469; ( 6 ) R. C. Paul R. D. Sharma and K. C. Malhotra Indian J . Chem. 1972,10,428; ( c ) R . Kurse and R. Paetzold Z . anorg. Chern. 1972,387 367. 92 ( a ) B. Buss and B. Krebs Inorg. Chem. 1971,10,2795; ( 6 ) L. Y. Y. Chan and F. W. B. Einstein J.C.S. Dalton 1972 316; ( c ) A. C . Hazell Acta Chem. Scand. 1972 26, 1510; (d) S. Syoyama K. Osaki and S .Kusanagi Inorg. Nuclear Chem. Letters 1972, 8 181. 93 ( a ) L. E. Alexander and I. R. Beattie J.C.S. Dalton 1972 1745; ( 6 ) G. A. Ozin and A. Vander Voet J . Mol. Structure 1971 10 397; (c) W. R. McWhinnie and M. G. Patel J.C.S. Dalton 1972 199; ( d ) W. R. McWhinnie and P. Thavornyutikarn ibid., p. 551 The Typical Elements 265 Normal-co-ordinate calculations on TeCl,Br have been carried out in the light of the recent X-ray work on TeCl 9 2 a and it has been concluded that the data can be best interpreted as arising from a mixture of at least the two high-symmetry conformers rather than just the low-symmetry C molecule as was reported last year.93b Far4.r. and Raman studies on diaryltellurium dihalides R,TeX, (Xe = C1 Br or I) have led to the conclusion that the $-bipyramidal structure with axial halogen atoms holds for a considerable variety of groups R.93c For aryltellurium trihalides the data suggest that some association occurs and that dimeric structures involving five-co-ordinate tellurium are most probable for chlorides and iodides.Some of the tribromides may be more associated.93d Mixed tellurium chloride azides Cl,TeN and Cl,Te(N,) have been prepared by the reaction of TeC1 with Me,SiN,. However with SCl and SeC1 reduc-tion occurs. The tellurium dichloride diazide reacted with Ph3P to give (Ph,P NPPh,),TeCl .94 Evaporation of solutions of tellurium halides in Me,NC(O)H and Me,NC(O)Me has given rise to the adducts TeX4,2.5Me,-NC(0)H (X = C1 or Br) TeI4,1.5Me,NC(O)H and TeX,,Me,NC(O)Me (X = C1 Br or I).95 SeF,Cl has been prepared for the first time by first preparing CsSeF from CsF and SeF and then condensing on ClS0,F at 77 K.The mixture is allowed to warm slowly to room temperature before the SeF,Cl is separated by fractional c~ndensation.~~" Physical properties n.m.r.96a and vibrational spectra,96a and thermodynamic properties96b have all been recorded. The reaction Of TeF with Me,SiOH in a sealed tube at room temperature results in the formation of TeF,OH by cleavage of the Si-0 bond rather than the 0-H bond as with alcohols. A parallel reaction occurs with triphenyl~ilanol.~~ Pentafluoro-orthoselenic acid has been synthesized from selenyl fluoride and a large excess of fluorosulphuric acid (SeO,F + 2HOS3F + KHF -+ HOSeF + H2S04 + KS0,F) and vapour pressure melting point boiling point and i.r.and n.m.r. spectra have been reported.98a The pentafluoro-orthoselenates M+SeOF,- (M = Li Na K Rb Cs or NH,) and Hg(OSeF,) have been pre-pared and characterized by n.m.r. and i.r. analysis,98b and F,Se-O-SO,-O-S0,F and F,Se-0-CO-CF have been prepared from the reaction of F,SeOH with SO and CF,COCl re~pectively.~~' New esters (70) of pentafluoro-orthotelluric acid have also been prepared by the route shown.99 The reactions were carried out at ice temperature in tetrachloroethylene (R = H or Me) or F,TeOH + N,CHR -+ F,TeOCH,R + N, (70) (R = H Me or C0,Et) 9 4 N. Wiberg G. Schwenk and K. H. Schmid Chem. Ber. 1972 105 1209. 9 5 9 6 ( a ) C. J. Schack R. D. Wilson and J. F. Hon Inorg. Chem. 1972 11 208; (6) K. 0. 9' G.W. Fraser and J. B. Millar J.C.S. Chem. Comm. 1972 1 1 1 3. M. Perier and G. Vincentini Anais Acad. brasil. Cienc. 1971,43 119. Christe C. J. Schack and E. C. Curtis ibid. p. 583. ( a ) K. Seppelt Angew. Chem. Internat. Edn. 1972,11,630; ( b ) K. Seppelt Chem. Ber., 1972 105 2431; (c) K. Seppelt ibid. p. 3131. 9 9 F. Sladky and H. Kropshofer Inorg. Nuclear Chem. Letters 1972 8 195 266 D. W. A . Sharp M . G. H . Wallbridge and J. H. Holloway methylene chloride (R = C0,Et). The SeV' species SeO,F, FSeO,(OR) [R = Me or Et] SeO,(OMe) and SeO,(OSiMe,) all form 1 1 complexes with the donors 2,2'-bipyridyl pyridine R,N and dioxan and these have been characterized by i.r. spectroscopy. The adducts are thermally labile; L,SeO,(OSiMe,) (L = donor ligand) thermally decomposes to L,(Me,Si),O and SeO but L,SeO,(OMe), and L,SeO,F(OEt) rearrange to give [L-Me]+ [MeOSeO,]- and [L-Et]+-[FSeOJ- respectively."' X-Ray data have shown that BaTeO,,H,O contains discrete TeO,'- ions with a mean Te-0 distance of 185.5 pm indicative of some double-bond character in the bonds."' Raman and i.r.spectra of solid M,TeO (M = K, Rb or Cs) are indicative of the presence of tetrahedral TeO groups and this has been confirmed by X-ray diffraction studies on the solid solutions formed in the K,TeO,-K,SO system.'02u Of the tellurates M2+Te04,- (M = Mg Ca Sr, Ba Cd or Pb) only MgTeO appears to be of a known structure type (cf. NiWO,). The rest are not isostructural with known structures of analogous tungstates, molybdates or uranates.'02' Exposure of crystalline selenates to 6oCo y-rays at 77 K gave the radicals SeO,- SeO,- SeO,- and Sea,,- and their electronic structures have been compared with those of other isoelectronic species.'03 Polonium.-The chemistry and physical properties of polonium have been authoritatively re~iewed.''~ No chemistry of the element has been reported this year but the vapour pressure of PoO in an oxygen atmosphere has been found to vary according to the relationship P/Torr = - 14.27 x 103/(T/K) + 12.57 (T varies between 991 and 1205 K).lo5 2 GroupVII An excellent comprehensive review on the vibrational spectra ofinorganic fluorides has been pub1ished.lo6 The bond dissociation energy of fluorine which was much debated last year,lo7' has been authoritatively discussed both from the experi-mental and theoretical standpoints.107b The most recent experimental results, obtained using a shock tube as a are in close agreement with earlier values using different technique^.'^^' Improved values for the adiabatic electron affinities of Cl, Br, I, and IBr have been obtained by making proper allowance for the influence of the thermal motion of the target gas,lo8' which had been neglected in earlier work.'08b There is now reasonable agreement between l o o R.Kurze and R. Paetzold Z . anorg. Chem. 1972,387 361. I o L B. R. Nielsen R. G. Hazell and S. E. Rasmussen Acta Chem. Scand. 1971 25 3037. l o 2 (a) P. Tarte and F. Leyder Compt. rend. 1971 273 C 852; ( 6 ) A. W. Sleight C. M. Foris and M. S. Licis Inorg. Chem. 1972 11 1157. ' 0 3 K. V. S. Rao and M.C. R. Symons J.C.S. Dalton 1972 147. ' 0 4 K. W. Bagnail in 'MTP Internat. Rev. Sci. Inorg. Chem. Ser. One' 1972 2 187, ed. C. C. Addison Butterworths London 1972. I o 5 R. H. Steinmeyer and C. H. Kershner J. Inorg. Nuclear Chem. 1971,33 2847. ' 0 6 D. J. Reynolds Adv. Fluorine Chem. 1973 6 1. ( a ) D. W. A. Sharp M. G. H. Wallbridge and J. H. Holloway Ann. Reports 1971, 68 A 354; (5) J. Berkowitz and A. C. Wahl Adv. Fluorine Chem. 1973 6 147; (c) J. Blauer and W. Solomon J . Chem. Phys. 1972,57 3587. l o * ( a ) A. P. M. Baede Physica 1972,59 541; ( b ) A. P. M. Baede and J. Los ibid. 1971, 52,422; A. M. C. Moutinho A. P. M. Baede and J. Los ibid. 1970,51,432 The Typical Elements 267 all the recent values obtained for the electron affinities of C1 and I, but values for Br still vary between 2.23 and 2.87 eV.'O*" The U.V.absorption spectrum of bromine vapour between 220 and 290 nm has been measured at 303 K and deviations from the Beer-Lambert law have been interpreted in terms of the formation of double molecules of Br . However the study shows that even saturated bromine vapour contains oiily about 1% of Br molecules.'09" The first spectra of Cl, Br, and I in the 1.84.0 nm region have been rep~rted.'"~ Raman spectra of liquid F and C1 have been shown to be very similar to gas-phase spectra though those for liquid chlorine at 238.6 K and 1 atm pressure are 7-8 cm- ' lower than the corresponding frequencies in the gas.'Og' The refractive indices of,fluorine (and HF) as a function of wavelength have been determined in order to facilitate the analysis of the flow field in a chemically reacting system of fluorine and hydrogen by interferometric methods.' ' A full set of thermodynamic equations for the heat capacity and vapour pressures of liquid and solid iodine have been obtained.' ' ' Fluorine manufacturing processes have been reviewed' and fluorine has been produced by the electrolysis of an anhydrous NH,F-HF electrolyte."2b The F + H reaction is of special theoretical interest because it is one of the simplest examples of an exothermic chemical reaction and since the FH system involves only 11 electrons the computation of a potential energy hypersurface to chemical accuracy may now be within reach of ab initio calculations.It is against this background that the results of the application of the i.r.chemiluminescence technique to obtain the initial vibrational rotational and translational energy distribution in the products of the exothermic reactions F + H and F + D, are of The method has also been applied to measure the distribution of energy amongst the products of the C1+ HI and C1+ DI reactions and prelim-inary results have been obtained for the reactions of Br + HI and C1+ HBr."3b It is clear that much more work in this and related areas will appear soon,especially in view of the recent extension of the molecular-beam method to reactions other than those of alkali-metal atoms.' 13' Molecular-beam methods have also been applied in a detailed study of the reaction dynamics of the H + X (X = Cl, Br, IC1 or IBr) family of reactions.It was ascertained that the dominant force controlling the dynamics is the halogen-halogen repul~ion."~" The H + X (X = C1 or Br)' 14b and H + F2114c l o g (a) W. Y. Wen and R. M. Noyes J . Phys. Chem. 1972,76 1017; (b) C. J. Humphreys and E. Paul jun.,J. Opt. Soc. Amer. 1972,62,432; ( c ) J. C. Barraland 0. Hartmanshenn, Compt. rend. 1972 274 B 981. A. B. Lindenberg Compt. rend. 1971 273 C 1017. (a) N. Watanabe Kagaku To Kogyo (Tokyo) 1972,23,615 ; (6) M. Caron C. Coquet, P. Coste and M. Rey Ger. Offen. 2 108 277/1971. ' I 3 (a) J. C. Polanyi and K. B. Woodall J . Chem. Phys. 1972,57 1574; (b) D. H. Maylotte, J. C. Polanyi and K. B. Woodall ibid. p. 1547; ( c ) J. B. Cross and N . C. Blais ibid., 197 1,55. 3970. ' l a ( a ) J . D. McDonald P.R. Le Breton Y . T. Lee and D. R. Herschbach J . Chem. Phys., 1972 56 769; (6) K. G. Anlauf D. S. Horne R. G. MacDonald J. C. Polanyi and K. B. Woodall ibid. 1972 57 1561; (c) J. C. Polanyi and J. J. Sloan ibid. p. 4988. 1 1 0 W. F. Rumpel G. Yanow and D. F. Penning J . Chem. Phys. 1972,57 3011. ' I 268 D. W. A . Sharp M. G. H . Wallbridge and J. H . Holloway reactions have also been examined by the i.r. chemiluminescence technique. The kinetics of the reaction between H and F have been studied by e.p.r. methods." 5 a and a study of the H,-Cl reaction in nickel flow-reactors has given reaction sequencies for both the gas-phase and surface reactions.' ' 5' Far-ix. spectra have been obtained of the charge-transfer complexes between 1X (X = I Br or C1) and a variety of organic sulphides.This is the first systematic study of such complexes with the sulphur atom as donor.'16' The dipole moments of iodine complexes with Me,SO and other oxygen-containing bases indicated the significance of the dipole moments of the oxygen lone pairs as well as the large contributions from the inductive effect.' 16' Relatively little seems to have been published this year on halogen anions, but e.s.r. observations of C1 -,adsorbed on the zeolites faujasite andmordenite,' ' 7 a and Br - in irradiated single crystals of the clathrate 4-p-hydroxyphenyl-2,2,4-trimethylchroman and 1,2-dibromo-l,l-difluoroethane' '" have been reported. More reviews on the chemistry of halogen and interhalogen cations have appeared.". ' '* The chlorination of aromatic compounds by HOCl has been the subject of many papers; however the most recent paper on the topic 'The last of Chlorinium Ion C1" ' I 9 has dismissed the popular intermediate by means of a thorough kinetic study.It is concluded that it is very improbable that C1+ is significantly involved in any thermal reaction ever studied in solution. As far as HOCl is concerned there are two reactive intermediates formed chlorine monoxide and the protonated species H,O-CI and these two together account for all the reactions. A melting point uersus mole-fraction investigation coupled with n.m.r. and i.r. examination of the I,-S,O,F system has confirmed the existence of I(SO,F) ISO,F and I,SO,F and established the existence of a new species I,(SO,F). In contrast to many other systems no evidence was obtained for The oxidation of bromine with S,O,F in solution in fluorosulphuric acid and in the super-acid system SbF5-3S03-HS0,F has produced the cations Brzf and Br,' together with BrS03F and Br(S0,F)3.'20a More evidence against claims that C1,' or ClF' are produced in SbF, HS0,F-SbF, or HF-SbF solutions has been obtained from an investigation of the reactions of ClF and C1F-Cl with the SbF-3SO3-HSO,F system.E.s.r. spectra of the solu-tions which were previously assigned to CIF' appear to be due to oxygen-containing species,' ,'' as has been suggested before.' ,'' Photoelectron spectra, obtained from the molecules I and Br, have been used to assign the electron 'Is ( a ) S . W. Rabideau H. G. Hecht and W. B. Lewis J . Magn. Resonance 1972 6 384; ( b ) L.S. Bernstein and L. F. Albright Amer. Inst. Chern. Engineers J . 1972 18 141. 'I6 ( a ) M. Yamada H. Saruyama and K. Aida Spectrochim. Acta 1972 28A 439; ( b ) L. Sobczyk and J. Danel J.C.S. Faraday I 1972 68 1544. '" ( a ) J. A. R. Coope C. L. Gardner C. A. McDowell and A. J. Pelman Mol. Phys., 1971,21 1043; (b) L. D. Kispert and J. Pearson J . Phys. Chem. 1972,76 133. R. J. Gillespie and M. J. Morton in 'MTP Internat. Rev. Sci. Inorg. Chem. Ser. One', 1972,3 199 ed. V. Gutmann Butterworths London 1972. ' I 9 C. G. Swain and D. R. Crist J . Amer. Chem. SOC. 1972 94 3195. 1 2 0 ( a ) R. Gillespie and M. J . Morton Inorg. Chem. 1972 11 586; (b) R. J. Gillespie and M. J. Morton ibid. p. 591; ( c ) R. S. Eachus T. P. Sleight and M. C. R. Symons, Nature 1969,222,769; (d) F.G. Herring and R. A. N. McLean Inorg. Chem. 1972,11, 1667 The Typical Elements 269 spectra of the cations 12+ and Br2+.120d The triatomic cation 13+ has been obtained for the first time in a solid compound I +AlC14- and has been charac-terized by n.q.r. methods.' 2'a The 19F n.m.r. spectrum of ClF + has been observed for the first time"lb and the new salt I2C1+SbCl6- has been prepared and shown I + I to contain the / \ cation.121c This is only the second interhalogen cation I c1 to be isolated which contains no fluorine. A crystal-structure determination of the 1 2 adduct formed by BrF and SbF has shown that the crystals contain infinite chains of discrete BrF4+ and Sb,F 1- ions coupled by relatively weak fluorine bridges.lZ2" A number of species containing BrF,' have been obtained by the reaction of BrF with various Lewis acids and tentative assignments of the vibrational spectra have been made.'226 The electrolysis of BrF with platinum electrodes results in the stepwise reduction of BrF,' to bromine.'22C The penta-atomic cation I s + has been characterized by n.q.r.in the solid A new and stable species C1F6+ has been characterized independently by two l a b ~ r a t o r i e s . ' ~ ~ " ~ The IF6+ ion has been studied by 19F n.m.r. in anhydrous HF.123C Avery useful guide to the treatment ofinjuriescaused by HF hasjust appeared.' 24 It has been concluded from 19F n.m.r. data that the normal H-F bond length is 95 & 3 ~ m . I ~ ' The orthorhombic form of HCI has been studied by X-ray and neutron diffraction' 26a and by Raman spectroscopy.' 26b*c No appreciable change to the cubic phase was detected in the crystal structure at the transition point (98 K).'26" The N02F-HF system which is similar to the NOF-HF system contains the adducts N02F,3.5HF N02F,4.0HF N02F,5.25HF and N02F.6.66HF (cf: page 233 ref.149).lZ7 It has been shown that some halogen fluorides can be salted out of solution from anhydrous HF by the presence of high concentrations of NaF.'28" Phase diagrams for the systems HF-MF (M = V Nb Ta or Sb) have been obtained and the stabilities of the complexes formed in the systems discussed. The complex SbF,,SHF is said to be the most stable.'28b Ab initio self-consistent-field calculations of potential-energy curves for the 1 + A1C14- .I 2 a ( a ) D. J. Merryman P. A. Edwards J. D. Corbett and R. E. McCarley J.C.S. Chem. Comm. 1972,779; ( 6 ) M. Brownstein and J. Shamir Canad. J. Chem. 1972,50,3409; ( c ) J. Shamir and M. Lustig Inorg. Nuclear Chem. Letters 1972 8 985. ''' ( a ) M. D. Lind and K. 0. Christe Inorg. Chem. 1972,11,608; ( b ) T. Surles A. Perkins, L. A. Quarterman H. H. Hyman and A. I. Popov J. Inorg. Nuclear Chem. 1972 34, 3561 ; ( c ) H. Meinert and U. Gross 2. Chem. 1972 12 150. I Z J ( a ) F. Q. Roberto Inorg. Nuclear Chem. Letters 1972 8 737; ( 6 ) K. 0. Christe ibid., p. 741 ; ( c ) M. Brownstein and H. Selig Inorg. Chem. 1972 11 658. l Z 4 A. J. Finkel Ado. Fluorine Chem. 1973 7 199. ''* S. P. Gabuda and Yu. V. Gagarinskii Doklady Akad. Nauk S.S.S.R. 1972,202 1065. ( a ) N.Niimura K. Shimaoka H. Motegi and S. Hoshino J. Phys. SOC. Japan 1972, 32 1019; ( b ) R. Heastie Chem. Phys. Letters 1972 15 613; (c) T. S. Sun and A. Anderson Spectroscopy Letters 197 1,4 377. ( a ) M. Brownstein and J. Shamir Inorg. Nuclear Chem. Letters 1971 7 997; ( 6 ) V. K. Ezhov Zhur. neorg. Khim. 1972 17 661. 1 2 ' F. See1 and V. Hartman J. Fluorine Chem. 1972 2 99 270 D. W. A . Sharp M . G. H . Wallbridge and J. H. Holloway ground and first-excited states of HF' have been ~erf0rmed.l~' The first direct experimental evidence for the angular fluoronium ions FH,+ FO,' and FHD+ has been obtained by vibrational spectroscopy and it has been shown that in the presence of liquid HF the ions are strongly solvated in the form (HF),H+.I3' The radiofrequency and microwave transitions of the K = 0 states of (HF),, HFDF and (DF) have been observed by the molecular-beam electric-resonance technique.The dimers have been shown to be non-linear and higher polymers may have cyclic structures since they appear to be n~n-polar.'~' Bond energies in FHF-,13," ClCHC1 BrHBr and IHI'32b and the vibrational frequencies for the three radicals'32b have been calculated. The IHI radical has been identified in the condensate after mixtures of iodine hydrogen and argon had been passed through a glow discharge and then condensed on to a window at 16 K. The i.r. spectrum showed that the radical has a linear symmetric (Dcoh) structure'32c like that of BrHBr. The free energy and enthalpy of the reactions X-(solv) + HCl(so1v) + HClX-(solv) have been determined from calorimetric measurements in the weak dipolar aprotic solvent sulpholane.The data com-bined with values of the heat of solution of HC1 have provided new minimum hydrogen-bond energies (58.2,44.8 and 33.5 kJ mol- ' respectively for C1- Br-, and I - ) for HClX-.'32d Inorganic hypofluorites have been reviewed.' 3 3 The kinetics and mechanism of the reaction C1,O + NOCl- C1 + N0,Cl have been studied spectrophotometrically in solution and the rate has been determined as -d[NOCl]/dt = k[Cl,O][NOCl] with k = 104.'6*0.25 Electron resonance spectra for BrO and I 0 have been obtained.' 3 5 a New potential-energy curve calculations for I 0 have produced a value for the dissociation energy which agrees well with the experi-mental value of 1.9 f 0.2 eV.135b The physical chemistry and mechanisms of many reactions involving C10, have been reviewed in E.s.r.studies have revealed C10 as the reaction product resulting from the electrolytic oxidation of perchlorate salts in ethereal solutions,'36b and BrO has been observed after 6oCo y-irradiation of various crystalline bromates and frozen aqueous glasses.' O 3 Pulse radiolysis of PhBr mol- 1 - 1 134 e( - 7 5 00 f 450)/R T 1 . J. Raftery and W. G. Richards J . Phys. (B) 1972 5 425. 1 3 0 M. Couzi J. C. Cornut and Pham Van Huong J . Chem. Phys. 1972,56,426. 1 3 ' T. R. Dyke B. J. Howard and W. Klemperer J . Chem. Phys. 1972,56 2442. L 3 2 (a) H. P. Dixon H. D. B. Jenkins and T. C. Waddington J . Chem. Phys. 1972 57, 4388; ( b ) D. G. Truhlar P. C. Olson and C.A. Parr ibid. p. 4479; ( c ) P. N. Noble, ibid. 1972 56 2088; ( d ) R. L. Benoit M. Rinfret and R. Domain Inorg. Chem., 1972 1 1 2603. 1 3 ' M. Lustig and J. M. Shreeve Adu. Fluorine Chem. 1973 7 175. 1 3 4 H. Martin J. Robisch H. D. Knauth and K. G. Prusseit Z . phys. Chem. (Frankfurt), 1972 77 227. 1 3 5 (a) J. M. Brown C. R. Byfleet B. J. Howard and D. K. Russell Mol. Phys. 1972, 23,457; ( b ) V. M. Trivedi and V. B. Gohel J . Phys. ( B ) 1972 5 L38. ' 3 6 ( a ) G. Gordon R. G. Kreffer and D. H. Rosenblatt Progr. Inorg. Chem. 1972 15, 201; ( b ) G. E. Glass and R. West Inorg. Chem. 1972 11,2847; ( c ) J. M. Bossy M. W. Leoni and R. E. Buehler Helv. Chim. Acta 1972 55 107 The Typical Elements 27 1 saturated with oxygen has also given rise to BrO, which was detected by its visible spectrum.' 36c Crystal-structure determinations on KIO,,HIO are in good agreement.'37a9 The HIO and 10 groups are pyramidal.Strong 0-1 e e - 0 interactions and electrostatic attractions between K + and 0'- give slabs which themselves are connected by hydrogen bonds. Defects in NaCIO single crystals induced by X-irradiation have been shown by e.s.r. methods to be due to ClO, ClO, and 0,- f0rmati0n.l~~ The BrO radical has been observed in various crystalline bromates and both BrO and possibly BrO,,- have been detected in BaSO, doped with bromate after subjection to 6oCo y-irradiation. ' O3 Vibrational spectra and force constants for ClO,- BrO - and 10,- in aqueous s01ution,'~~~ the i.r. spectra for anhydrous gaseous liquid and solid Cl,07 and the Raman spectrum for liquid C1207' 39b have been obtained.The intermediate formation of 10,- and the subsequent conversion into 10,- have been observed by i.r. methods in a very neat experiment in which KMnO and KI were mixed and pressed into a KI The Raman spectra of anhydrous HF solutions containing ClOF alone or together with SbF, AsF, or BF have provided evidence for ClOF,+ (sym-metry group C,).140 Chlorine oxide trifluoride ClF,O which was first mentioned in the open literature in 1970,'41a has been the subject of a number of Preparations by the direct fluorination of C1,0 NaClO, or ClONO or by subjecting F toa glow dischargein the presence by the photochemical combination of the elements or from halogen oxide fluorides and F, ClF or ClF, or from ClF and O2l4'' have been described.Physical pr~perties,'~'' vibrational s p e ~ t r a ' ~ ' ~ ~ and thermodynamic properties 141d have been discussed in detail. It has been demonstrated that the main reactions of the compound involve fluorination oxygenation or both oxygenation and fluorination of the ~ u b s t r a t e s ' ~ ' ~ and that the compound is amphoteric forming complexes with strong Lewis acids and bases.' 41s For example with alkali-metal fluorides, MF,ClF,O (M = Cs Rb or K) adducts are formed ; with SbF, AsF, and BF,, crystalline 1 1 adducts are produced; and with SiF, the complex SiF4,2C1F,O is given.','/ With PtF, fluorine is liberated to give the new complex C1F20+-PtF -. l4 l e The ClF,O- ion has been fully characterized by vibrational spectro-scopy and has a C, structure analogous to that of ClF or XeOF Reactions 1 3 ' ( a ) G.Kemper A. Vos and H. M. Rietveld Canad. J . Chern. 1972 50 1134; ( 6 ) 1 3 ' 0. Vinther J . Chem. Phys. 1972 57 183. 1 3 ' ( a ) D. J . Gardiner R. B. Girling and R. E. Hester J . Mol. Structure 1972 13 105; ( b ) A. C . Pavia J. Roziere and J. Potier Compt. rend. 1971 273 C 781 ; ( c ) T. Gym-kowski D. G . Lambert and H. s. Kimmel J . Inorg. Nuclear Chern. 1972 34 1841. 140 R. Bougon J. Isabey and P. Plurien Cornpt. rend. 1971 273 C 4!5. 14' ( a ) R. Bougon J. Isabey and P. Plurien Cumpt. rend. 1970 271 C 1366; ( 6 ) D. Pilipovich C. B. Lindahl C. Schack R. D. Wilson and K. 0. Christe Znurg. Chem., 1972 11 2189; ( c ) D. Pilipovich H. H. Rogers and R. D. Wilson ibid. p. 2192; (0 K.0. Christe and E. C. Curtis ibid. p. 2196; ( e ) C. J. Schack C. B. Lindahl D. Pilipo-vich and K. 0. Christe ibid. p. 2201 ; (f) K. 0. Christe C. J. Schack and D. Pilipovich, ibid. 1972 11 2205; ( g ) K. 0. Christe and E. C. Curtis ibid. p. 2209; (h) R. Bougon, Compt. rend. 1972 274 C 698. L. Y . Y. Chan and F. W. B. Einstein ibid. 1971 49 468 272 D. W. A . Sharp M. G. H. Wallbridge and J. H . Holloway of CIOF with PF and ClF have given new complexes which have been formulated as ClOF,+PF,- and ClOF,+ClF,- on the basis of i.r. and Raman ~ p e c t r a . ' ~ ' ~ The complexes ClO,SbF and C102Sb,F,6 are claimed to result from the reaction of SbF with CI0,F,'42" and reaction of C10,F with PtF has given the adduct ClO,F,+PtF,- in which the cation has been characterized by its i.r.The 10,F- radical has been observed in y-irradiated crystals of KIO,F and the possible structures of the ion have been d i s c ~ s s e d . ' ~ ~ Molecular orbital calculations carried out on CIOF 5 c indicate considerable 3d orbital participation in the bonding of the central atom. The enthalpy of formation of Br0,F (AH;1298.15 = 112.1 f 1.1 kJmol-') and other thermo-dynamic properties have been obtained from calorimetric rneasurement~.'~~ Traces of the new species ClO,F have been identified by i.r. in the 131 K fraction of the condensate from the reaction of excess of FNO at 195 K with a mixture of Enthalpies of formation for MIO,F (M = Na K Rb or NH,) have been ~ b t a i n e d . ' ~ ~ " . ~ The i.r. and Raman spectra of the Na' and K+ salts are similar, showing that the shape of the IO,F,- ion is the same in each compound.'46b The shape of the ClO,F,- ion can be derived from a trigonal bipyramid (symmetry C2J with the two fluorine atoms occupying the axial positions while the oxygens and a lone pair are equatorial.'46' Following the identification of ClF by matrix i.r.spectroscopy preliminary evidence for the species Cl,F Cl,F, and CI,F has now been rep~rted.'~' A comprehensive systematic study of the reactions of ClF ClF ClF and C10,F with monofunctional and bifunctional hydroxy-compounds has been made'48" and the primary hydrolysis product of the reaction of ClF with water has been shown to be C10F.'48b The dipole moment of ICl has been deduced from Stark-effect measurements in a microwave study of 13%1 and 137C1.'49 A new preparative method for pure BrF involves the reaction of fluorine with elemental bromine in CC1,F.'" Nitrosyl tetrachloroiodate NOICl, has been prepared from iodine chlorine and NOCl at 233 K and identified at low tempera-tures by Raman spectroscopy.Warming to 248 K resulted in the decomposition C1o2 +PtF6 - and 10 % C1F202 + ptF6-.l4, ( a ) Z. K . Nikitina and V. Ya. Rosolovskii Izvest. Akad. Nauk S.S.S.R. Ser. Khim., 1972 750; (b) K. 0. Christe Inorg. Nuclear Chem. Letters 1972 8 453. 1 4 3 S. Subramanian and M. T. Rogers J. Phys. Chem. 1971 75 3479. L44 G. K. Johnson P. A. G. O'Hare and E. H. Appelman Inorg. Chem. 1972 11 800. 1 4 5 K. 0. Christe Inorg. Nuclear Chem. Letters 1972 8 457. ( a ) A. Finch P. N . Gates and M.A. Jenkinson J.C.S. Dalton 1972,2044; (b) A. Finch, P. N. Gates and M. A. Jenkinson J . Fluorine Chem 1972 2 1 1 1 ; ( c ) K. 0. Christe and E. C. Curtis Inorg. Chem. 1972 11 35. 14' M. R. Clarke W. H. Fletcher G . Mamantov E. J. Vasini and D. G. Vickroy Inorg. Nuclear Chem. Letters 1972 8 61 1 . 1 4 ' (a) K. 0. Christe Inorg. Chem. 1972 11 1220; (b) T. D. Cooper F. N. Dost and C. H. Wang J. Inorg. Nuclear Chem. 1972 34 3564. 1 4 9 E. Herbst and W. Steinmetz J. Chem. Phys. 1972 56 5342. E. Lehmann D. Naumann and M. Schmeisser Z . anorg. Chem. 1972 388 1 The Typical Elements 273 of the salt to NOICl and Cl, and at 323 K NOCl and ICl were produced.'"" The reactions of CsIF and CsIF with excess of (CF,CO),O led to the final products CsI(OCOCF,) and CS,I(OCOCF,)~ respectively.' " The almost square-planar ICl,- ions in the crystal structure of HIC1,,4H2O have been shown to be packed in layers between sheets consisting of a hydrogen-bonded hydrate network.151c New 1 3 adducts of alkali-metal fluorides with IF have been reported and their vibrational spectra obtained.It has been confirmed that the IF6- ion does not have a symmetry higher than C, .l Trifluoromethyliodine(v) tetra-fluoride CF,IF, has been prepared by the oxidation of CF,I with ClF at 195K.'52b Substitutions in IF to give IF,OR (R = Me or Et) have been achieved using Me,SiOR or related compounds in much the same way that has been widely used to prepare aryloxy- and alkoxy-derivatives of covalent fluorides.' 52c The preparation of BrF by the reaction of BrF with fluorine in the presence of MBrF (M = alkali metal) at 380-610 K has been ~ 1 a i m e d .I ~ ~ The Raman spectra of IF in liquid and gaseous anhydrous HF have been and a new study of the vibrational spectra of gaseous IF has confirmed that the molecule undergoes minor dynamic distortions from D, symmetry.' 5 4 Reactions of bromine(1) fluorosulphate with gold and platinum have been described.' 5 5 Iodine(II1) perchlorate I(OCIO,) has been prepared by the low-temperature reaction of iodine with excess ClOClO and Cs+I(0C1O3),- has been synthesized from CsI and ClOClO .156 The chemistry of astatine has been reviewed.'57u Oxidation of astatide and astatine by Cr,O,,- in dilute aqueous solutions results in the production of positively charged ions of astatine.' 5 7 b 3 GroupVIII New reviews stressing the most recent advances in noble-gas chemistry have been published,' and the preparation and physical and chemical properties of KrF have been described.' 58c In the latter paper much preliminary Russian work is mentioned which has not appeared in the open literature.1 5 1 ( a ) J. P. Huvenne and P. Legrand Compt. rend. 1972,274 C 2073; (b) D. Naumann, M. Schmeisser and R. Scheele J. Fluorine Chem. 1972 1 321 ; (c) R. J. Bateman and L. R. Bateman J . Amer. Chem. Sac. 1972 94 1 1 30. ( a ) K. 0. Christe Inorg. Chem. 1972 11 1215; (6) 0. R. Chambers G. Oates and J. M. Winfield J.C.S. Chem. Comm. 1972 839; ( c ) G. Oates and J. M. Winfield, Inorg. Nuclear Chem. Letters 1972 8 1093. 1 5 3 C. E. Fogle and R. T. Rewick U.S.P.3615206/1971. s 4 H. H. Eysel and K. Seppelt J . Chem. Phys. 1972,56 508 1 . 1 5 6 K. 0. Christe and C. J. Schack Inorg. Chem. 1972,11 1682. Is' ( a ) E. H. Appelman in 'MTP Internat. Rev. Sci. Inorg. Chem. Ser. One' 1972 3, 181 ed. V. Gutmann Butterworths London 1972; (6) D. K. Tung I. Dudova and V. Khalkin Joint Inst. Nuclear Invest. Rep. 1971 JINR-P12-5644 (Nuclear Sci. Abs., 1971 25 26209). l S 8 ( a ) F. Sladky in 'MTP Internat. Rev. Sci. Inorg. Chem. Ser. One' 1972 ed. V. Gutmann Butterworths London 1972; ( b ) F. Sladky Allg. prakt. Chem. 1971 22, 213; (c) V. N. Prusakov and V. B. Sokolov At. Energ. 1971 31 259. W. M. Johnson R. Dev and G. H. Cady Inorg. Chem. 1972 11 2260 274 D. W. A . Sharp M . G. H . Wallbridge and J. H. Holloway All the known stable noble-gas compounds contain the noble gas bound either to fluorine or oxygen.However since the discovery of the noble gases the notion that xenon-boron compounds might exist has always seemed attractive' 59a and it has now been shown that O,BF reacts with xenon at 173 K to give a white solid which decomposes at 243 K. Raman and i.r. evidence has shown that this F / \ solid has the structure F-Xe-B .159b F Theoretical calculations suggest that both the related hypothetical molecule Xe-BF and XeB+ salts are unlikely but that zwitterions such as +XeBloH9,-might be possible.' 59c Ab initio calculations on linear symmetric KrF have confirmed Coulson's earlier proposal that the Kr-F bond is ionic in nature near the equilibrium separation and becomes covalent at larger separations.16' A brief report on studies of the KrF,-BrF system mentions that if SbF is added KrF2,2SbF, may be isolated from the mixture but no new compounds can be obtained.161a It has been shown that KrF2,2SbFs has a stretching wavenumber of v(Kr-F+) = 626 cm- ' and may be formulated KrF+Sb,F -.161b*c The oxidizing properties of KrF,' l a and KrF+ ' ,' b* ' have also been discussed and it has been shown that KrF+ will oxidize XeOF to XeOF,+.161' The ideal-gas heat capacities at constant pressure free-energy functions and entropies for XeF, XeF, XeF, XeOF, XeO,F, and XeOF at 1OO-lOOO K have been obtained from spectroscopic data.',, Fluorination of organic species by XeF has been discussed with reference to radical-cation intermediate^'^^" and the mechanisms inv01ved.l~~~ The results of many studies on xenon difluoride complexes have appeared.' 64a-c These include the new species XeF ,XeOF,; XeF ,XeF ,AsF ; XeF ,2XeF6 ,2AsF5 ;' 64a [XeF+],[MF6]2- (M = Ti Zr or Sn).164b XeF2,2BrF, and XeF2,9MFs (M = I s 9 ( a ) J.H. Holloway 'Noble Gas Chemistry' Methuen London 1968 p. 49; ( b ) C. T. Goetschel and K. R. Loos J. Amer. Chem. SOC. 1972,94 3018; (c) J. F. Liebman and L. C. Allen Inorg. Chem. 1972 11 1143. (a) V. N. Prusakov and V. B. Sokolov 2hur.fiz. Khim. 1971,452950; (b) N. Bartlett, D. Gibler D. McKee R. Mews and M. Wechsberg Abstracts of The Sixth Inter-national Symposium on Fluorine Chemistry Durham July 1971 paper C24; (c) D. E. McKee C. J. Adams A. Zalkin and N. Bartlett J.C.S. Chem. Comm.1973,26. 1 6 2 S. A. Kudchadker and A. P. Kudchadker Proc. Indian Acad. Sci. Sect. A 1971 73, 261. 1 6 3 ( a ) J. Burdon I. W. Parsons and J. C. Tatlow Tetrahedron 1972,28,43; ( 6 ) R. Filler, H. H. Hyman and M. J. Shaw J. Org. Chem. 1971,36,2917. 1 6 4 ( a ) N. Bartlett and M. Wechsberg 2. anorg. Chem. 1971 385 5 ; (b) V. N. Legasov, V. N. Prusakhov and B. B. Tchaivanov Report of I. V. Khurtchatov Institute for Atomic Energy IAE-2185 Moscow 1972; (c) B. B. Tchaivanov V. A. Legasov V. N. Prusakov and V. B. Sokholov ibid. IAE-2186 Moscow 1972. ''' P. S. Bagus B. Liu and H. F. Schaefer tert. J. Amer. Chem. Soc. 1972,94,6635 The Typical Elements 275 Br or I).',,' Infrared spectra of 2XeF,,RuF and XeF,,RuF and i.r.165b and Raman'65' data of 2XeF2,SbF,;XeF,,SbF,;2XeF,,3SbF ; and XeF2,2SbF have been published.Reactions of CrF with xenon and XeF have been studied and a non-volatile solid XeCr,F,, has been obtained as well as XeF,.',," Reactions of xenon fluorides with UF and UF have been reported.'66b The new species FXeOPOF and Xe(OPOF,) have been obtained in high yield by the reaction of XeF with P203F4 at 295 K in CC1,F.'67 The structure of xenon(u) fluoride fluorosulphate has established the existence of discrete FXeOS0,F molecules. The F-Xe-0 angle is 177.4(3)" and the Xe-0 bond length is 215.5(8) pm.'68 The recently prepared pentafluoro-orthoselenic acidg8" has been shown to react with XeF to give FXeOSeF and Xe(OSeF,)2.'69 XeF has been used to oxidize neptunium-(v) and -@I) to neptunium(vI1) in alkaline solution.70 The use of XeF to ~ynthesize'~' Xe2FI1+AUF6- is perhaps one of the most significant developments in noble-gas chemistry of late. Although several laboratories have recognized the potential of noble-gas fluorides as powerful fluorinating agents this is one of the first successes. New ground has also been opened up by theoretical and spectroscopic studies on XeF,. The suggestion that, in the vapour XeF is a mixture of three molecular isomers differing in electronic state and nuclear g e ~ m e t r y ' ~ ~ " seems to be borne out by detailed ir. Raman and U.V. spectroscopic investigation^.'^^^ The reaction of UF with XeF has pro-duced the complex XeF,,UF ,' 66b and X-ray investigations suggest that the uF molecules are inserted into a tetrameric XeF lattice.'73 Earlier reports that F,Xe(OSO,F) and F,Xe(OSO,F) had been prepared have been shown to be in~orrect"~ so that at present only three fluorosulphates, Xe(OSO,F) FXeOSO,F and F,XeOSO,F are known.Fluoride glasses containing Xev' have been described.' 7 5 Xenon dioxide tetrafluoride XeO,F has been prepared by the reaction of XeO,F with XeF in XeOF solvent.'76" Raman and i.r. spectra of the matrix-isolated molecule have shown that it has D, symmetry.' 766 The new complexes ' 6 5 ( a ) V. N. Prusakov V. B. Sokolov and B. B. Chaivanov Zhur. priklad. Spekrroskopii, 1972,17 114; ( b ) B. B. Chaivanov 2hur.priklad. Khim. 1972,46,23; (c) G. S. Baronov, N. P. Egorov A. N. Sopikov and B. B. Chaivanov Zhur. f i z . Khim. 1972,46 18. 166 ( a ) J. Slivnik and B. Zemva 2. anorg. Chem.1971 385 137; (6) M. Bohinc and B. Frlec J . Inorg. Nuclear Chem. 1972 34 2942. 1 6 7 M. Eisenberg and D. D. Desmarteau Inorg. Chem. 1972 11 1901 1 6 * N. Bartlett M. Wechsberg G. R. Jones and R. D. Burbank Inorg. Chem. 1972 11, 1124. K. Seppelt Angew. Chem. Internat. Edn. 1972 11 723. K. Leary and N. Bartlett J.C.S. Chem. Comm. 1972,903. and H. Kim ibid. p. 5042. 2938. D. D. Desmarteau and M. Eisenberg Inorg. Chem. 1972,11 2641. "' E. F. Rieblin P. E. Blaszyk and D. W. Smith U.S.P. 3 650 779/1972. ( a ) J. L. Huston J . Amer. Chem. SOC. 1971 93 5255; (6) H. H. Claassen and J. L. Huston J . Chem. Phys. 1971,55 1505. 170 V. D. Klimov V. N. Prusakov and V. B. Sokolov Radiokhimzya 1971 13 725. 1 7 ' L 7 2 (a) G. L. Goodman J . Chem. Phys. 1972,56,5038; ( b ) H.H. Claassen G. L. Goodman, 1 7 3 B. Frlec M. Bohinc P. Charpin and M. Drifford J . Inorg. Nuclear Chem. 1972 34 276 D. W. A . Sharp M . G. H. Wallbridge and J. H. Holloway XeO,F+Sb,F and XeOF3+Sb,F 1- have been synthesized from XeO,F and XeOF, respectively and the "F n.m.r. and Raman spectra of the XeOF,+ and XeO,F+ ions have been interpreted. 1 7 7 The vibrational spectra and force field of XeO have been reported,178a and rules for the estimation of the frequency ratio ~ 1 / ~ 3 of the symmetric and anti-symmetric stretching vibrations of tetrahedral transition-metal 0x0-anions have been extended to cover 0x0-anions of the main-group elements and in particular ~ O X ~ O . ' ~ ~ ' It has been shown that gaseous radon can be oxidized to a solid by oxidants such as ClF ClF ClF their bromine analogues or IF7.The radon compound is probably RnF2.17'" The work has been extended to show that Rn also reacts spontaneously with solid complexes such as ClF,SbF and BrF,Sb,F to yield non-volatile ions and compounds and the possibilities of applying this to the removal of Rn from air in uranium mines has been discussed.179b '" R. J. Gillespie B. Landa and G. J. Schrobilgen J.C.S. Chem. Comm. 1972 607. ''* (a) R. S. McDowell and L. B. Asprey J . Chem. Phys. 1972,57 3062; (6) E. J. Baran, Z. Naturforsch 1972 27b IOOO. (a) L. Stein U.S.P. 3660300/1972; (b) L. Stein Science 1972 175 1463