5 N P As Sb and Bi By D. A. ARMITAGE Department of Chemistry King's College London Strand London WC2R 2LS UK 1 Halogen Derivatives Calculations regarding the vibrational stability of covalent NF and NF have been re-evaluated. They support NF adopting D, symmetry but severe ligand crowding would suggest the more stable ionic structure NF;F-. though this would be unstable relative to NF and F, even at -142°C.' An extensive range of halophosphonium salts has been made and their vibrational spectra compared. They include PX4-,F,+ (X = H D; n = 04) Cl,-,Br,PSBr+-AsF (n = 0-3) X,FPSMe'MF (X = Br CI) XF,PSMe+SbF (X = Br C1 F) and Me,PCl(SMe);-,Cl-. Structures have been determined for Me,PSMe+T and MeP(SMe)Cll SbC1 .3 Magic-angle spinning 31 P NMR spectroscopy of Me,PXl- (X = C1 Br) provided support4 for the presence of isomers of both MePCllC1- and Me,PCl;Cl-.The mixed cations MePCl,Br+ MePClBr,' ,and Me,PCl; have also been observed. The Br adduct of Ph,P has been shown to have a covalent four-coordinate structure Ph,P-Br-Br analogous to the iodine adducts Ph,M-1-1 (M = P AS).^ Reaction of cobalt powder with Me,PI gives the five-coordinate CO(III) complex (Me,P),CoI,; Bu;PI yields the 'frozen transition state' complex [(Bu;PI)~(,LI- I)][ (Bu~PPI)(p-I)Co13] .6 AsF forms a range of nitrile adducts and complexes with 1,3,5-triazine to give 1 1 2 1 and 3 1 adducts.' Oxidative fluorination of AsCI with XeF'AsF; gives the arsonium salt FAsCli AsF .8 Reacting the anions As,Cli- and AsSBr, as their Ph4P+ salts with M(CO) (M = Cr W) in thfgives Ph,P+AsX,(thf); (X = C1 Br) as major products.The D4,-like structures show no lone-pair stereochemical activity but K. 0.Christe and W. W. Wilson J. Am. Chem. So(,. 1992. 114. 9934. R. Minkwitz D. Lennhoff W. Sawodny. and H. Hartner Z. Narurforsch. Ted B. 1992. 47 1661; R. Minkwitz T. Hertel and G.Medger Z. .4norg. Ally. Chem.. 1992,615,114; R. Minkwitz P. Garzarek and G. Medger ibid 1992 612 40. R. Minkwitz G. Medger. R. Greth. and H. Preut Z. Narurjorsch. Teil B 1992 47 1653. R. K. Harris A. Root P.N. Gates and A. S. Muir Spectrochim. Acta A 1992 48 1371. N. Rricklenank S. M. Godfrey. A. G. Mxkie. C. A. McAuliffe and R. G. Pritchard J. Chem. Soc. Chem. Commun.. 1992 355. C.A. McAuliffe. S. M. Godfrey A.G. Mxkie and R.G.Pritchard Anyrw. Chrm.,Int. Ed. Enyl.. 1992.31 919. I. C. Tornieporth-Oetting and T. M. Klapotke Chem. Ber. 1992. 125. 407; I.C. Tornieporth-Oetting. T. M. Klapotke. U. Behrens and P. S. White. J. Chem. Soc. Dalton Trans. 1992. 2055. R. Minkwitz and W. Molsbeck Z. Anory. Ally. Chem. 1992 607 175. 53 D. A. Armitage the As-X bonds are longer than single.' Oxidation of (Ph,P),AS,Cl with ozone gives Ph,P+AsCl and Ph,PCI.H,AsO, while (Ph,P),Sb,Cl gives Ph,P+SbCl; and (Ph,P),(SbOC1,)2~2CH2C12.'o The haloarsenates As,X (X = Br I) have novel structures in which a central AsX octahedron shares two faces of common vertex with two face-bridged terminal octahedra in which the bridge bonds are longer than the terminal ones. * ' Hydrogen fluoride reacts with R,N+SbCI; to give a range of mixed anions containing two to six fluorine atoms as established by 12'Sb and 19F NMR spectroscopy.'2 While Ph,SbF gives only Ph,SbCl upon reaction with chlorine the bromine reaction gives a range of mixed products including Ph,SbBr,F-SbPh,Br, which possesses a fluorine bridge.Hydrolysis of this gives (Ph,SbBrF),O which itself contains a strong intramolecular fluorine bridge and has antimony in both five and six-coordination states as does the original bromination product.' The anions Ph,SbX (X = CI Br) show V-trigonal bipyramidal structures with axial halogens. With Ph,Sb,X;-(X = C1 Br) however coordination is square pyramidal resulting in a wide-angled Sb-X-Sb bridge. l4 CH,(SbCl,) adds bromide to give [(BrC1,Sb),CH,l2 -,which itself adds Br to each Sb site at -78 "C.' 15-crown-5 complexes with SbBr, MeSbX (X = CI Br) and PhSbBr,.The structures of the bro- mides show all five oxygen atoms to be bonding thus making Sb eight-coordinate.16 MeSbI adopts a structure with association through iodine bridges thus forming a chair-like structure. It reacts with Me,Sb+I- to form the adducts (Me,Sb+),- MeSbIi- which comprise tetrahedral cations and square pyramidal anions.' The stibines (Me,XCH,),Sb (X = C Si) add iodine and the resultant adducts decompose at 170°C to R,SbI. Further addition of iodine gives R,SbI, which decomposes at room temperature to RSbI,. The halides Me,CCH,SbBr and (Me,CCH,),SbI can be readily reduced and provide intermediates for the vapour phase deposition of antimony.' [18]AneS forms a 1 1 complex with BiCl that has all six sulfur atoms coordinating in an unusual S-shaped conformation and possessing three-fold symmetry.' 'BiBr forms a 2 1 charge transfer complex with [2.2]paracyclophane in which the aryl rings n-bond to BiBr which has a halogen-bridged chain structure.20 Condensing Me,P into solid BiBr gives Bi,Br,(PMe,) in low yield as a centro- symmetric edge-shared bi-octahedral bromide-bridged dimer with cis phosphine ligands one of which is trans to a bridging bromine.Bi,Br,(PMe,Ph),(OPMe,Ph) results with PhMe,P (and adventitious oxygen).,' BiCl complexes with 15-crown-5 B. Siewert and U. Muller Z. Naturforsch. Teil B 1992 47 680. lo K. Ruhlandt-Senge A.-D. Bacher and U.Muller Z. Naturfimch. Ted B 1992 47 1677 I' W.S. Sheldrick and J. Kiefer Z. Naturforsch. Teil B 1992 47 1079. M. F. A. Dove and J.C. P. Sanders J. Chem. SOC. Dalton Trans. 1992 331 1. I3 S. P. Bone M. J. Begley and D. B. Sowerby J. Chem. SOC. Dalton Trans. 1992 2085. l4 W. S. Sheldrick and C. Martin Z. Naturforsch. Teil B 1992 47 919. Is S. Kraft and M. Wieber Z. Anory. Ally. Chem. 1992 607,157. l6 M. Schafer J. Pebler and K. Dehnicke Z. Anorg. Ally. Chem. 1992 611 149. " H. J. Breunig K. H. Ebert S. Guelec M. Drager D. B. Sowerby M. J. Begley and U. Behrens J. Organornet. Chem. 1992 427 39. D.G. Hendershot J.C. Pazik C. George and A.D. Berry Organometallics. 1992 11 2163; D.G. Hendershot J. C. Pazik and A. D. Berry Chem. Muter. 1992 4 833 (Chem. Ah. 1992 117 131 282).l9 G. R. Willey M.T. Lakin and N. W. Alcock J. Chem. Soc. Dalton Trans. 1992 1339. 1. M. Vezzosi L. P. Battaglia and A. B. Corradi J. Chem. Soc. Dalton Trans. 1992 375. W. Clegg R. J. Errington R. J. Flynn M. E. Green,D. C. R. Hockless N.C. Norman,V. C.Gibson,and K. Tavakkoli. J. Chem. Soc. Dalton Trans. 1992. 1753. N P As Sb and Bi 55 and 18-crown-6 while BiBr with the latter gives the ionic product (18-crown- 6)BiBrlBiBri. The anion is polymeric as is that in (pentaethylene glycol)BiI~Bi,I; .22 The thf complex PhBiX,(thf) (X = Br I) crystallizes as a halogen bridged one-dimensional polymer with square pyramidal coordination and apical phenyl groups; reaction of the iodide with Et,NT gives the anion Ph,Bi,Ii- as a centrosymmetric edge-shared square pyramid.Ph,BiBr(thf) and Ph,BiBr; show V/-trigonal bipyramidal structures with both phenyl groups and lone pairs being eq~atorial.'~ The condensed phase Bi 1414 comprises a one-dimensional ribbon of chair Bi interconnected rings that is six rings wide with alternate bismuth atoms on the edge of the ribbon bonding to two iodine atoms.24 2 Transition Metal Clusters The dinitrogen complex [(Cp:ZrN,),p-N,] reacts with phosphine to give the dimeric phosphide bridged derivative [CpzZr(H)PH,],. This reacts with alkenes and PH to generate primary alkyl phosphines under the mildest conditions reported to date.25 The bisphosphido complex (CpTZrPHMes) loses MesPH to give the first early transition metal phosphinidene complex CpTZr=PMes which decomposes to the isomeric phosphametallocycle through C-H addition across the Zr=P bond.It also adds MesPH with H elimination to give the diphosphametallocycle. All three compounds add MeCN to give P and N substituted metallocycles.26 Cp,Zr generated from Cp,ZrCl and Bu"Li in situ oxidatively adds PhPH to give an intermediate complex which itself decomposes through C-H activation to give the Zr(m) diphosphide and fulvalenide bridged complex. Ar*PH (Ar* = 2,4,6-tri-t-butyl-phenyl) gives a trimeric phosphide-capped Zr(1v) species thus providing a rare example of a tricapping phosphorus atom formed via Ar*-P cleavage.27 Bu',P, on heating with either Fe(CO) or Fe,(CO), gives BU\P,Fe,(cO) with a P chain end-bonding to the Fe,(CO) residue; the use of Fe,(CO) at room temperature also yields Bu',P,Fe(CO),Fe,(CO), in which the central P atom bonds to the Fe(CO) residue.28 The reaction between NiCI and Bu\P in the presence of (Me,Si),P leads to [Ni(PBu'),] in which Ni is surrounded by a hexagonal plane of six P atoms., White phosphorus reacts with Fe,(CO) in benzene under reflux to give the complex (Fe(CO),(pP,)},(p-Fe,(CO)6}2in which almost square P units (P-P bonds 21 3.0 and 21 2.4 pm j chelate to Fe(CO) in the same plane.This is orthogonal to that of the two Fe,(CO) units.30 When white phosphorus reacts with Bu'C5H,Rh(CO), one P-P bond of P is cleaved and in the presence of (thf)Cr(CO), Bu'C,H,R~(CO)P,[C~(CO)~],,in which the P ligand has a butterfly-like bicyclo[ 1.1.O]butane structure is obtained.22 R. D. Rogers A. H. Bond S. Aguinaga. and A. Reyes J.Am. Chem. Soc. 1992 114 2967. 23 W. Clegg R. J. Errington G. A. Fisher L). C. R. Hockless. N. C. Norman A. G. Orpen and S. E. Stratford J.Chem. SOC. Dalton Trans. 1992 1967. 24 E. V. Dikarev B.A. Popovkin and A. V. Shevelkov. Z. Anorg. Allg. Chrm. 1992 612 118. 25 S. Nielsen-Marsh R. J. Crowte and P.G. Edwards J.Chem. Soc.. Chem. Commun.. 1992 699. 26 Z. Hou and D. W. Stephan J. Am. Ch(1m. Soc. 1992 114 10088. 21 J. Ho and D. W. Stephan Oryanometallics 1992 11. 1014. 28 Y. W. Li M.G. Newton N. K. Bhattacharyya. and R. B. King Inory. Chem. 1992 31 2069. 29 R. Ahlrichs D. Fenske H. Oesen and U. Schneider Anyew. Chem. Int. Ed. Engl. 1992 31 323. 30 M. Scheer M. Dargatz K. Schenzel and P.G. Jones J.Organomet. Chem. 1992 435 123. 31 M. Scheer C. Troitzsch and P. G. Jones. Angew. Chem. Int. Ed. Engl. 1992 31 1377. 56 D.A. Armitage In decalin at 170”C Cp“Rh(CO),[Cp” = 1,3-Bu:C,H3] and E (E = P As) give (Cp”Rh),E,-E,(RhCp”) and [(Cp”Rh)(p,q2 :q2-E2)], the former involving the P, ligand acting as both a o and n donor ligand to Rh., By way of contrast heating Cp”Nb(CO) with P gives the triple decker sandwich Cp”Nb(p-q6 :q6-P,)NbCp” in which the P ligand behaves as a double n-ally1 donor with four short and two long P-P bonds. The ability of P and As to undergo far greater out-of-plane distortions than benzene provides for a greater variety of structures in these triple decker sandwich compounds.33 Photolysing [Cp4Ni(p-C0)] (Cp4 = PrbC,H) with P or heating with As gives CpiNi,E and Cp4Ni(q3-E,) (E = P As).The structure of the first of these involves a Ni,As trigonal prism with the Ni atoms at opposite corners of one rectangle., Cp*M(q’-E,) (E = P As; M = Fe Ru) n-complexes with M’(CO) residues (M’ = Cr Mo) through the E ring. Three of the Fe derivatives of both P and As rings show equal bond lengths within the E rings that are shorter than usual single bond lengths while for the two derivatives Cp*Fe(p-q5 ,As,)M‘(CO)~ the As-As bonds appear slightly longer in the Mo than Cr derivatives.,’ Phosphenium and arsenium complexes CpW(CO),=ER and the methylphos- phinidene unit from (MeP) react to give a metallo substituted heter~cycle.,~ The phosphine and arsine complexes (CO),CrEPh,H -,(m = 1,2) react with alkynes uia insertion into the E-H bond to give vinyl c~mplexes.~’ (p3-As)(RC,H,),Mo,(CO) (R = H Me) and Cp,Mo,(CO),As coordinate to iron carbonyl residues to give p4-As derivatives; mixed p-As clusters result from p3-AsCp,Mo,(CO) and Cp,Ni,(CO) or (Ph,P),PtC2H,.38 The As tetrahedron can be progressively opened by Cp*Co(CO) residues to give Cp*Co(CO)(q” ’-As,) [Cp*Co(CO)],(p-q’ ’-AS,) and Cp*Co(p-q4 ’:‘-As,)Co(CO)Cp* the last of which involves a cis-As chain acting both as a n-type ligand to Cp*Co and as a terminal o-bonded ligand to Cp*Co(CO) residues.39 CptSm dealkylates Bu”,b in thf to give the complex (CptSm),(p-q2 :q2:q’-Sb,).thf which contains the bent Sb;- anion and also has 1,2 and 1,3 chelation to two Sm entities and coordinates to the third; the Sb-Sb bond lengths of 268.8 pm are shorter than usual single bond lengths.,’ CpMo(C0); and SbCl react to give the Mo-Sb cluster (p4-Sb)2Cp,Mo,(CO), in which each Sb atom is o-bonded to CpMo(CO) and [CpMo(CO),] residues and coordinated to CpMo(CO) and Mo(CO) residue^.^' A range of mononuclear polydentate Sb and Bi substituted complexes of Fe Cr Mo and W has been made., 32 0.J.Scherer B. Hoebel and G. Wolrnershauser Angew. Chem. Int. Ed. Engl.. 1992 31 1027. 33 A. C. Reddy E. D. Jernmis 0.J. Scherer R. Winter G. Heckrnan and G. Wolrnershauser Organomera/-lics 1992 11 3894. 34 0.J. Scherer J. Braun P. Walther and G. Wolrnershauser Chem. Ber.. 1992..125 2661. 35 9. Rink O.J. Scherer. G. Heckman and G. Wolrnershauser. Chem. Ber..1992. 125. 1011. 36 W. Malisch K. Hindahl and R. Schernrn. Chem. Ber.. 1992 125 2027. 37 H. Lang and U. Lay J. Organomet. Chem. 1992. 441 389. 3R M. Gorzellik 9. Nuber,and M. L. Zeig1er.J. Orgunornet. Chem. 1992,436,207;M.Gorzellik 9.Nuber T. Bohm and M. L. Ziegler ihid. 1992 429 173. 39 0.J. Scherer K. Pfeiffer and G. Wolrnershauser Chem. Ber.. 1992 125 2367. 40 W. J. Evans S.L. Gonzales and J. W. Ziller. J. Chem. Soc.. Chem. Commun. 1992 1138. 41 M. Gorzellik 9. Nuber and M. L. Ziegler J. Organornet. Chem. 1992 431. 171. 42 K. Merzweiler and L. Brands. Z. Naturjorsch. Teil B 1992,47,978; F. Bringewski G. Huttner. W. Imhof and L. Zsolnai J. Organornet. Chem. 1992 439 33; W. Clegg N.A. Cornpton R. J. Errington G.A. Fisher D. C. R. Hockless N. C. Norman N.A. L. Williams S.E. Stratford. S.J. Nichols. P. S.Jarrett and A. G. Orpen J. Chem. Soc. Dalton 7ran.s. 1992 193; W. Clegg N. A. Cornpton R. J. Errington. G.A. Fisher D.C. R. Hockless N.C. Norman A.G. Orpen. and S.E. Stratford hid.. 1992 3515. N P As Sh and Bi Ni6(CO):; and BiCl react to give Ni,,Bi,(CO); (n = 2 3) which comprises a pl'-Ni unit atom contained in a Ni,,Bi ic~sahedron.~~ 3 Pnictogen Clusters Heating KP or KAs with Cs,P, and MX (M = Ga In; X = P As) to 950 K gives the alkali metal derivatives of MP3- or MAS:- respectively in which the anions are polymeric and contain four-membered rings connected in a spiro fashion as in SiS,., CUP comprises 2D anions of boat-like P rings (cf-black phosphorus with chair rings) with one P-P bond broken per Pi- unit.Cu(rkCu(~) bonding results cia P-bridging in Cu,P rings and through-space interactions of dt s and p orbitals.45 The structure of Ca,,GaAs, comprises tetrahedral GaAs units and linear As units with a hyper- valent three-centre four-electron bond and provides the first example of a discrete hypervalent Group- 15 linear anion., [Na(2,2,2-crypt)l3Sb;1 comprises the anion with idealized D symmetry similar to that found in and calculated for P:;.,' Calculations indicate that the Mulliken population of the 'A ground states of P to Bi shows little difference in s and p orbital population and only a 0.18 to 0.16 contribution for d orbitals. With Bi there is a full contribution from the 6s orbital electrons due to relativistic stabili~ation.~~ With P6 the benzvalene and prismane-like isomers are the most stable with the planar D, benzene analogue the least stable.For P, the polycyclic structure (1 ) is the most stable but this is less by 49 kcal mol- ' than two P molecules.49 Disilenes ring open P and As to give the bicyclo[ 1.1 .O]butane analogue (2) that for As being formed cia the tricyclic intermediate (3).50Ph,P,As, which contains alternating pnictogen atoms complexes with the Mo(CO) residue as a twist-boat conformation with phosphorus atoms at positions 1 and 4 in the ring showing scrambling to have preceded complex f~rmation.~ ' 4 Chalcogen Derivatives The dithionitryl salt SNS' AsF, which results from the reaction between sg S,N, and AsF in liquid SO with a trace of Br, readily adds successively to each CN group of KC(CN), the monoadduct crystallizing as polymeric sheets of the dithiadiazole 43 V.G. Albano. F. Demartin M. C. Iapalucci,G. Longoni. M. Monari.and P. Zanello. J. Chem. Soc. Dalron Trans.. 1992 497. 44 M. Somer. K. Peters and H.-G. von Schnering. Z.Anory. Ally. Chem.. 1992. 613. 19. 45 P. Alemany S. Alvarez. M.-H. Whangbo and M. Evain. Inory. Chrm.. 1992. 31. 119. 46 R. F. Gallup C. Y. Fong and S. M. Kauzlarich. Inory. Chrm.. 1992. 31. 115. 47 U. Bolle and W. Tremel. J. Chem. So(,..Chem. Commun.. 1992. 91 R. 0.Jones and G. Seifert. J. Chem. Phys. 1992 % 7564. 4R H. Zhang and K. Balasubramanian J Chem. Phy.5.. 1992. 97. 3437. 49 D. S. Warren and B. M. Gimarc. J. Am. Chem. Soc.. 1992.114.5378; R.Janoschek Chem. Ber.. 1992.125. 2687. 50 A. D. Fanta R. P. Tan. N. M. Comerlato. M. Driess. D. R. Powell. and R. West. Inory. Chim. Ac,ro. 1992. 198-200 733. 51 A. L. Rheingold and F. P. Arnold Inory. Chim. Actu 1992. 198 200. 139. D.A. Armitage unit and in the triadduct the dication adopts C, symmetry. A structure determination of the benzothiarsolium cation supports pn-bonding between arsenic and A range of cyclic thiophosphates P,S (n = 10,9,7),results from white phosphorus and polysulfides; the TR spectra readily distinguish them. [Me,P(S)],P has a pyramidal structure with P-P bonds of 222.6 pm and a mean PPP angle of 105.7 0.s3 P,Se reacts with Sei- to give P,Sei- comprising P(v) in a P,Se chair ring which with Fe(CO) gives the complex [Fe2(CO),(PSe5),l2 -; the P(=Se)(Se-),(Se;) units bridge the two Fe atoms through both the two P=Se bonds and the isolated Se atoms.As,Seg-reacts with M(CO) to generate [M(CO),(As3Se,),12- while As,Seg- and M(CO) give [M(AsS~,),]~-.~~ Two isomers of each of cr-P,S,SeI and a-P,SSe,I have been identified by 31P and 71Se NMR spectroscopy; a systematic change in chemical shift and coupling constants was found for the series u-P,Ch,I (Ch = ~halcogen).~~ Irradiating Ph,P+ As,SCI in the presence of W(CO) gives Ph,PCl.4As4S and Ph,PWOCI,.thf; heating Cp”,o,(CO) (Cp” = EtMe,C,) and As,S gives both As and S substituted molybdenum complexes i.e. As,MoCp”(CO), As,Mo,Cp”,CO), and Cp”,o,X (X = S, 02S, os3).56 As,Cli -(X = C1 Br) reacts with Na,S to give As,SXg -(4) which upon further reaction is converted to SASS (5).57 (Ph,P),Sb3Cl, reacts with Na,S to give Ph,P+Sb,SCl; and (Ph,P+)2Sb2Cli- and with Na,S or Na,S to form (Ph,P+),- Sb,SClg-.58 (Bu‘NSiMe,),Se and SbCl give the cage-like derivative Se(SbCl),- (NBu‘) (6).s9 5 Organic Phosphorus Derivatives The application of transition metals in the synthesis of organophosphorus compounds has been reviewed.60 A reinvestigation of the structure of the tetracyanoethylene 52 E.G. Awere and J. Passmore J. Chem.Soc. Dalton Trans. 1992 1343; A. J. Bannister I. Lavender J. M. Rawson and W. Clegg ihid.,1992,859 N. Burford T. M. Parks B. W. Royan J. F. Richardson and P. S. White Can. J. Chem. 1992 70 703. 53 H. Falius. A. Schliephake. and D.Schomburg Z. Anorg. Allg. Chem. 1992 611. 141 L. Andrews. C. Thompson and M. C. Demarcq Inorg. Chem. 1992,31. 3173; M. Scheer and P. G. Jones J. Organomet. Chem. 1992 434 57. 54 J. Zhao W. T. Pennington. and J. W. Kolis. J. Chem. Soc. Chem. Comrnun. 1992,265;S. C. O’Neal W. T. Pennington and J. W. Kolis Inorg. Chem. 1992 31 888. 55 R. Blachnik P. Loennecke and B. W. Tattershall J. Chem. Soc.. Dalton Trans. 1992 3105. 56 B. Siewert and U. Miiller Z. Anorg. Allg. Chem.,1992,609,77; M. Gorzellik B. Nuber and M. L. Ziegler J. Organomet. Chem. 1992 429 153. ” B. Siewert and U. Muller Z. Anorg. Allg. Chem. 1992 609,82. B. Siewert and U. Miiller Z. Anorg. Ally. Chern.. 1992 609.89. ”) M. Bjorgvinsson H. W. Roesky F. Pauer and G. M. Sheldrick Chem. Ber. 1992 125 767.6o F. Mathey A. Marinetti and F. Mercier. SYNLETT 1992 363. N P As Sb and Bi adduct of Ph,P showed it to have the N-(heptacyanocyclopent-1-enyl)triphenylphos-phoranimine structure (equation l).61 The ability of phosphorus in organofluorophosphanes to behave both as an electrophile and a nucleophile determines both their disproportionation and reactions with aldehydes. Thus Bu;PF disproportionates via the P(III)-P(v)intermediate Bu",PF,(Bu") and reacts with PhCHO to give BU",OCHP~PF,(BU"),.~~ Reacting (Bu\P),PLi with BrCH,CH,Br gives Bu\PP=P(Br)(Bu'), which decomposes to a mixture of cyclophosphanes at 20 "C through the phosphinidene intermediate Bu',PP but gives the hexaphosphane [(Bu; P),P] at -20 "Cin toluene as yellow crystals.The structure indicates steric hindrance at the tertiary P atoms with angles of 115.7 ".63 1,2-Di-t-butyldiphosphine(7) disproportionates sequentially on warming to give first the triphosphane H,(Bu'P) (8) then the t-butylphosphinocyclotetraphosphane (9)which further reacts with (7)and (8)to lengthen the side chain thus giving (10).This further decomposes to (Bu'P) and the bicyclo[3.1 .O]hexaphosphane BukP (1 1) which itself yields BuiP (12) and Bu',P (13).64 Other polycyclophosphanes result from the thermolysis of Pr'PCl,/P,/Mg. 3,4,7,10,1l-Pr~-pentacyclo[7.4.0.0.~~60.5*1 30.87' 2]tridecaphosphane (14) (phosphorus skeleton only shown) occurs as two configurational isomers with different spacial arrangements at P-3 and is part of the Hittorf's phosphorus tubular structure.65 The tetraisopropyloctadecaphosphane(4) 8,14,16,18-tetraisopropyloctacyclo 10.4*90.5~70.6~'00.12~17]octadecaphosphane 113.2.1.0.2,'30.3*' (15) comprises P ,(5) and P,(3) structural units joined through a common P bridge and occurs as two configurational isomers with different spacial arrangements at P(8).66 Hexaiso- propyloctadecaphosphane(6) (1 6) also results from Pr'PCI,/P,/Mg and comprises " T.Mohan R. 0.Day and R. R. Holmes Inory. Chem. 1992 31. 2271. 62 J. Haenel G. Ohms and L. Riesel Z. Anory. Allg. Chem. 1992 607 161. 63 G. Fritz H. Goesmann and B. Mayer Z. Anorg. Ally. Chrm. 1992 607 26. 64 M. Baudler and H. Tschabunin Z. Anorg. Allg. Chem. 1992 617 31. 65 M. Baudler H. Jachow and K.-F. Tebbe. Z. Anory.Allg. Chem.. 1992,614 17. 66 M. Baudler W. Oehlert A. Kmieciak and A. Floruss Z. Anorg. Ally. Chern. 1992 611 43. D.A. Armitage 10 16 P11(5)and P,(5) units and is the first example of a heptacyclopolyphosphane 13.2.1.0.2,130.3*' 2.1 ']oc-5,7,8,14,16,18-hexaisopropylheptacyclo[ r0.4*90.6*'00.' tadecaphosphane. Compound (16) closely resembles (15) except that no bonding between P-5 and P-7.67Hexaisopropylicosaphosphane(6) occurs as a mixture of two constitutional isomers (17) and (1 8) in equal abundance; one 6,7,9,16,17,20-10.4980.5*100.'3*' hexaisopropyloctacyclo[ 10.8.0.0.23140.39' 80.'5*19]icosaphosphane,is a mixture of diastereomers (17) and the other 7,9,15,17,19,20-hexaisopropylocta-cyclo[14.2.1.15*80.2~'40.3*'20.4*100.6*1 'O."*' *]icosaphosphane a mixture of configur-ational isomers (18).68 54 20 19 '' M.Baudler H. Jachow and J. Hasenbach Z. Anorg. Allg. Chem. 1992 608 28. M. Baudler H. Jachow. W. Oehlert A. Kmieciak and A. Floruss. Z. Anorg. AUg. Chem.. 1992. 616 19. N P As Sh and Bi 61 6 Organoantimony and Bismuth Compounds The synthetic applications of organoantimony compounds have been reviewed.69 Bu‘SbMe can be made from SbCl in a one-pot synthesis from Bu‘MgC1 (-50 T) then MeMgBr (0“C)in ether and its thermal decomposition involves homolysis of the But-Sb bond and is unaffected by the addition of Me3Ga.” Condensing two moles of Ar,SbLiwith R,SbBr (R = Ph tolyl Me) gives the tristibanes R,Sb(SbAr,) with a trigonal bipyramidal structure and equatorial Ar,Sb The structure of Mes,Sb shows a trigonal pyramidal structure; Mes,Sb adopts a trans conformation with Sb-Sb bond lengths of 284.9~117.~~ Reducing Pr’SbBr with Mg gives (Pr’Sb) (x = 4 5) both of which are stable in solution at room temperature under an inert atmosphere but decompose on either warming or isolation as solids.The proton NMR spectrum of (Pr’Sb) supports the presence of both rings in solution.73 [(Me,Si),CHSb], however is stable as a solid and occurs as orange-red crystals that are air-stable even above their melting point (130 “C). The structural studies indicate a folded four-membered ring with trans substituents. Tristibines (R,Sb),SbR’ result as equilibria in solution from (R’Sb) and R,Sb (R = Ph R‘ = Et) and the tetrastibine (Ph,SbSbEt) also forms in solution.Cyclic stibines or distibines readily cleave the Se-Se or Te-Te bonds in diselenides or ditellurides to give the appropriate Sb-Se or Sb-Te deri~ative.~ An electron diffraction study of Me,Sb supports a trigonal bipyramidal structure. The first stibepine results from the appropriate stannepine with SbCl and can be alkylated at the Sb-Cl bond; these derivatives are thermally unstable reverting to the naphthalene and unidentified Sb derivatives in a few hours. The structure of the stibepine was confirmed by X-ray crystallography and is thermally more stable than the As analogue.’ Rh(1) catalyses the dearylation of Ar,Bi in the presence of CO to give the diarylketone; in methanol methyl benzoates Unlike most heavy metal azides Ar,Bi(N,) is reasonably thermally stable and oxidizes acyl isocyanates to give the N-arylcarbamoyl azide as the main product along with urea biuret and tetrazol- 5-0ne.~~ series of chiral mixed triaryl bismuthines results from the sulfonyl- A controlled selective iododearylation of o-Bu‘SO,C,H,Bitol, followed by successive acylati~n.~~ 1-Phenyl-2,5-dimethylbismole gives red-black crystals of the tetramethyldibismafer- rocene analogue upon dephenylation and reaction with FeCl,.A crystal-structure study shows a ferrocene-like array with Bi . . . Bi contacts of 368.8 pm close to that found between molecules of the green 2,2’,5,5’-tetramethylbibismole (365.9 6y Y.-Z. Huang Acc. Chem. Res. 1992. 25 182. ’(I R. W. Gedridge Jr. Orgunometullics 1991 11,967; D.S. Cao. C. H. Chen C. W. Hill S. H. Li. and G. B. Stringfellow J. Electron. Muter.. 1992 21 583 (Chem. Ah.. 1992 117 1 I1 715). ” N.K. Jha and P. Sharma J. Chem. Soc.. Chrm. Commun.. 1992 1447. ’’ M. Ates H. J. Breunig K. H. Ebert R. Kaller. M. Drager. and U. Rehrens %. Nururforsch.. Teil B 1992.47. 503. 73 M. Am H.J. Breunig K. Ebert S. Gulec R. Kaller and M. Drager. Oryunometullics 1992. 11. 145. 74 H. J. Breunig. S. Gulec. and R. Kaller Phosphorus. Sulphur. Silicon Relnr. Elm. 1992 67 33. ” C. Pulham A. Haaland A. Hammel K. Rypdal. H. P. Verne and H. V. Volden. Angrw. Chem. Inr. Ed. Enyl. 1992 31 1464; A. J. Ashe 111 L. Goossen. J. W. Kampf. and H. Konishi. ihid. 1992. 31 1642. 76 C.S. Cho T. Ohe 0.Itoh and S. Uemura J. Chem.Soc. Chem. Commun.. 1992 453. ’’ H. Suzuki C. Nakaya and Y. Matano. J. Chem. Res. (S) 1992 34. ’’ H. Suzuki and T. Murafuji. J. Chem. Soc.. Chem. Commun.. 1992. 1143. 7Y A. J. Ashe 111 J. W. Kampf. D. B. Puranik and S. M. Al-Taweel Oryunometullics 1992 11 2743. D.A. Armitage A range of dihydrodibenzo[b,e]bismines has been prepared for Bi(m) and Bi(v).80 Structure determinations suggest a transannular interaction between Bi and the heteroatom at position 5 providing the stabilization of CI-Bi and allyl-Bi bonds. The octasubstituted bistiboles and bibismoles result from the appropriate zirconacyclopen- tadiene with PhSbCI, PhBiBr, or BiBr, followed by reductive coupling. The bibis- moles are thermochroic but not the stiboles and in contrast with the less substituted 2,2’,5,5’-tetramethylbipnictides which are thermochroic for both Sb and Bi.81 7 Multiple Bonds to Carbon Further analogies between P=C and C=C double bonds have been reviewed as has the oligomerization of phosphaalkynes to phosphacubanes.82 The first example of a complex of a cyaphide (19) (phosphorus analogue of cyanide) has been shown to result from the 2-phosphavinylplatinum derivative (20) and successive Pd(0) and Pt(0) complex-mediated reactions.A structure determination shows a bridged cyaphide with a C-P bond length (166.6 pm) longer than in the parent phosphaalkynes and similar to that in the q2-phosphaalkyne complexes (equation 2).83 c1 ClI#tC(Cl)=PAr* pdL4-ClLPdAr* + ClkPtC=P LPtLI PL C24 (2) (20) L = Et3P p PtL (1 9) Fluorine substituted phosphaalkenes result from the gas-phase thermol-ysis of stannyl phosphines Me,SnP(R)NMe (R = CF or C,F,) and readily oligomerize or undergo [2 + 41 cycloaddition to ~yclopentadiene.~~ CF,P=CXF (X = F OR) give phosphorus ylides Me,P=C(X)P(F)CF, with PMe,; condensing Ph,PCH,R+Br-with Ph,P=CRPCI gives the phosphenium chlorides Ph,P=CRPCR=PPh (R =aryl) which also result from Ph,P=CRSiMe and PCI,.Na,X (X = S Se) and Ph,P=C(Ph)PCI give the monomeric Ph,P=C(Ph)PX with P=X multiple bonds.85 The phosphorus ylide H,C=PH has been shown to be stable in the gas phase; Bu\CIP=CPh occurs as yellow crystals containing three independent molecules in the unit cell with the P-Cl bond length increasing with increased eclipsing of the p-orbital in the ylide carbon atom with the P-Cl bond.AICI removes chloride to give the methylenephosphonium cation.86 (E,E)-and (E,Z)-3,4-(Ar*phosphinidene),cy-clobutene can be prepared by desilylating the 1,2-bissilylcyclobutene or thermally no H. Suzuki T. Murafuji and N. Azuma J. Chem. Soc. Perkin Truns. I 1992 1593. ni R. E. v. H. Spence D. P. Hsu and S. L. Buchwaid. Orqunometullics 1992. 11 3492. ” F. Mathey Acc. Chem. Res. 1992 25 90 M. Regitz. Bull. Soc. Chim. Belq. 1992 101 359. n3 H. Jun V.G. Young Jr. and R. J. Angelici. J. Am. Chem. Soc.. 1992 114. 10064. n4 J. Grobe D. Le Van S. Martin and J. Szameitat Z. Nuturfi,r.sch. Teil B 1992 47 321. n5 J. Grobe D. Le Van U. Althoff and G. Lange Chem. Ber. 1992,125,567;A. Schmidpeter and G.Jochern Tetrahedron Lett.1992 33 471. n6 H. Keck W. Kuchen P. Tornrnes J. K. Terlouw and T. Wong Anyew. Chem. Int. Ed. Engl. 1992,31,86; H. Grutzmacher and H. Pritzkow. ihid. 1992 31 99. N P As Sb and Bi isomerizing Ar* P=C=CH-CH=C=PAr* the bissilyl (E,E) derivative readily chelates to an Mo(CO) unit.'7 The aminophosphacyclobutadiene complex (CO),Ni(~'-p2-(Pr~NCP),)NI(CO), has one phosphorus atom of the four-membered ring complexing with both Ni(CO) residues; the C-P bonds are longer at this P atom (185 pm) than at the other uncomplexed P atom (178 pm). Molecular orbital calculations have been used to substantiate the photoelectron spectrum of the diphosphacyclobutadiene complex of Fe(CO) and CpCo residues.'* The 1A5,3L5-diphosphete [(Me,N),PCH] gives complexes with GeCI, SnCl, and W(CO), in all cases bonding occurs at carbon to give the zwitterion structure (21).2-Hetero- 1A5,3i5-diphosphabenzenes(22)complex with Mo(CO) residues through the P-X-P unit (equation 3).89 Me I (Ph,P),Pd dechlorinates 2,4,6-Bu',C,H2P=CCI to give the corresponding phos- phaalkyne quantitatively. The microwave spectrum of P-CCl shows a C-P bond length of 155.4pm." The molecular structure of BUT-P shows an almost linear skeleton with the CFP bond 154.2 pm while the signs of all the coupling constants to phosphorus in the ' NMR spectrum are positive." The spirocyclotrimerization of Bu'C-P in the presence of AICI gibes a betaine structure (23) which with DMSO to remove AICI, followed by a homo-Diels-Alder reaction with Bu'CEP gives the tetraphosphaheterocycle (24) (equation 4) isomeric with the tetraphosphacubane analogue .92 Lithiation of Cp,ZrCI followed by treatment with Bu'C-P gives the correspond- ing diphosphazirconabicycles which with C,Cl yield the tetraphosphacubane (Bu'CP),.This complexes with Fe,(CO), and subsequent demetallation leads to the diphosphete complex (Bu'CP),Fe(CO) and (Bu'P),F~(CO),.'~ '' K. Toyota. K. Tashiro M. Yoshifuji and S. Nagase Bull. Chem. SOC.Jpn 1992,65 2297; K. Toyota K. Tashiro M. Yoshifuji I. Miyahara A. Hayashi and K. Hirotsu J. Organomet. Chem. 1992 431 C35. 88 J. Grobe D. Le Van M. Hegemann B. Krebs and M. Lage Angew. Chem. Int. Ed. Engl. 1992,31.95;R. Gleiter I. Hyla-Kryspin P. Binger and M. Regitz Organometallics.1992 11 177. H9 E. Fluck M. Spahn G. Heckmann and H. Borrmann Z. Anorg. Allg. Chem. 1992,612,56;S. F. Gamper and H. Schmidbaur Organometallics 1992 11 2863. yo V. D. Romanenko M. Sanchez T. V. Sarina M. R. Mazieres and R. Wolf Tetrahedron Lett. 1992 33 2981; S. Firth S. Khalaf and H. W. Kroto J. Chem. Soc. Faraday Trans. 1992 88 3393. 91 A. N. Chernega M. Y. Antipin Y.T. Struchkov M. F. Meidine and J. F. Nixon. Hererout. Chem. 1991.2 665; B. Wrackmeyer Z. Nuturjbrsch. Teil B 1992. 47 437. 92 B. Breit U. Bergstrasser G. Maas and M. Regitz Angew. Chem. Inr. Ed. Engl. 1992 31 1055. 93 T. Wettling B. Geissler R. Schneider S. Barth P. Binger and M. Regitz. Angew. Chem. fnt. Ed. Engl. 1992 31 758; M. Birkel J. Schulz. U. Bergstrasser and M. Regitz ihid.1992 31 879. D.A. Arrnituge BU‘ ‘B u‘ (23) (24) Radical catalysed ring expansion of 1,2-ArT- 1,2-diphosphaspirocyclopentanegives the phosphacyclobutane (25),its P-oxide and the 1,4-diphosphanorbornadiene(26).94 Coupling CIP=C(R)SiMe with cyclopropenylidene phosphanes gives the new class of phosphapolyenes (27) with 2 ge~metry.’~ 8 Pictogen-Pnictogen Multiple Bonds and Catenation The diphosphenes Cp*P=PCp* and Cp*P=PAr* react with diazomethanes to give diphosphiranes via a [2 + 3]cycloadduct intermediate. Cp*As=PAr* behaves simi- larly to give products with the bulky substituents trans ~rientated.~~ A range of ql-and q2-complexes results from such diph~sphenes,~’ while reaction with the carbonyl anions Cp*M(CO); gives Cp*M(CO),P=PAr* and the tetraphosphabicyclobutane CPTP,.~~ Coupling (CO),Mn(H)PPh,H with Ar*AsCl using BuLi gives the novel manganacyclopropane (28)which has a short P-As bond length of 229 pm (equation 5).99 The phosphinidene complexes Cp(CO),M=PMes[M’(CO),Cp] (M = M’ = Mo W) add sulfur or selenium across the M=P double bond to give three-membered y4 C.Garot.G. Moghadam. J. P. Declercq. A. Dubourg and M. Konig .4ngew. Chem.,Inr. Ed. Engl. 1992 31. 625. 95 B. Breit. H. Mernmesheimer R. Boese. and M. Regitz. Chem. Ber. 1992 125. 729. L)6 P. Jutri and S. Opiela. Z. Anorg. AIlg. Chem.. 1992 610. 75. ’’ P. Jutzi. U. Meyer. S. Opiela. B. Neurnann and H.-G. Stammler. J. Organomer. Chem. 1992. 439 279; K. B. Dillon and H. P. Goodwin ihid.. 1992. 429. 169. ” P.Jutzi and S. Opiela J. Organomet. Chem. 1992. 431 C29. 9Y E. Lindner. P. Fisahn. R. Fawzi. and M. Steirnann Z. Nufur-orsch..TZ! B. 1992. 47 1798. N P As Sb and Bi phosphametallocycles. * O0 The reaction of the diphosphenyl complex Cp*(CO),FeP= PMes* with RC(O)N=NC(O)R gives the oxadiazaphospholene (29) through [l + 41 cycloaddition; A '-1,2,4-triazoline-3,5-diones give the first 1,2-diaza-3,4-diphos-phetidines (30) in benzene but in ether give the tetraphosphacyclododecadienes (31).' An excess of N-methylmaleimide induces P=P cleavage to give the phosphine (32) with succinimidyl and bicyclo[3.1 .O]-1-aza-4-phosphahexane-2,6-dion-3-y1 sub-stituents.lo2 0 9 Phosphorus-substituted Rings Phosphorus-substituted eight-membered rings have been reviewed.lo3 Calculations suggest remarkable stability for 1-fluoro-1H-phosphirene; the phos- phaC3lradialene (33) results from the 1-phospha- 1,2,3-butatriene (34) and dich- lorocarbene (equation 6).lo4 Calculated and observed diphosphirane dipole moments both indicate trans-isomers when large substituents are present but predict cis-isomers for less bulky groups. Addition of carbene to the rr-system of diphosphenes gives the monohalo diphos- phirane which can be ring opened photolytically to give 1,3-diphosphapropenes which with RMgX yield substituted 1,3-diphosphapropenes and dienes. Dihalodiphos- phiranes give 1,3-dipho~phallenes.'~~ (Me,Si),NLi dehydrohalogenates PhCH,-I"" U.-A. Hirth W. Malisch and H. Kab J. Organomet. Chem. 1992,439 C20.lo' L. Weber H. Bastian A. Miiller and H. Bogge 2.Naturforsch.. Teil B. 1992,47,23 1;L. Weber H. Bastian R. Boese H.-G. Stammler and B. Neumann Chem. Ber. 1992. 25 1821. lo2 L. Weber M. Frebel and R. Boese 2. Anorg. Ally. Chem. 1992,607. 139. lo3 R. P. Arshinova Phosphorus Sulphur Silicon Relat. Elem. 1992 68 155. '04 M. T. Nguyen H. Vansweevelt and L.G. Vanquickenborne Chem. Ber. 1992 125,923; I. Miyahara A. Hayashi K. Hirotsu M. Yoshifuji H. Yoshimura and K. Toyota Polyhedron 1992. 11. 385. C. Tachon M. Gouygou M. Kiinig M. J. Herve D. Gonbeau and G. Pfister-Guillouzo Inorg. Chem. 1992 31 2414; J.-P. Fayet D. Mermillod-Blardet C. Tachon G. Etemad-Moghadam and M. Konig. Can. J. Chem. 1992 70 2834; R. El-Ouatib C. Garot. G. Etemad-Moghadam and M. Konig J.Organomet. Chem. 1992. 436 169. D.A. Armitage (33) (Et,N)P(F)=CHPh to give the 1,i5,3i5-diphosphete as the cis isomer and the phosphirane (35) (equation 7).lo6 Photolysing Ar*P(N,) gives the phosphinidene which rearranges to the phosphain- dane through C-H insertion (equation 8).' O7 Thermolysing 1-benzyl- 1-phosphadihyd-roazulene in the presence of Pt/C gives 1 -phosphaazulene while the 2-benzyl derivative results on heating in xylene.lo8 Calculations on the aromaticity of phosphorus analogues of the cyclopentadienyl anion show PC,H to retain 86% of the aromaticity ofC,H and remarkably P; to be as aromatic as C,H .lo9 Mass spectra support the existence of the phosphatropylium and phosphabenzylium ions formed from benzene and P' (from PI3).ll0 Treating P,C,Bu and P,C,Bu\H with an excess of sulfur gives mono- and trisulfur adducts respectively.The trisulfide adds ethanol (equation 9).l1 The tetraphosphafulvalene dianions (36) (isoelectronic with tetrathiafulvalene dications) react with sulfur to give the dithiophosphinate derivative (37) or with q5-CpFe(q6-xylene)+ to give the ferrocene-like derivative (38) which further chelates to a Mo(CO) residue (Scheme l).' ' Penta- and hexaphosphaferrocenes coordinate to W(CO) and Ru,(CO), residues. The coupling of (38) with glutamoyl chloride and Io6 E. Fluck R. Braun A. Miiller and H. Bogge Z. Anorg. Allg. Chem. 1992 609 99. lo' A.H. Cowley F. Gabbai R. Schluter and D. Atwood J. Am. Chem. Soc. 1992. 114 3142. lo' G. Mark1 and J. Reindl Tetrahedron Lett.1992 33 5495. lo' E. J. P. Malar J. Org. Chem. 1992 57 3694. 'lo C.A. Muedas D. Schroeder D. Suelzle and H. Schwarz J. Am. Chem. Soc. 1992 114 7582. 'I1 R. Bartsch P. B. Hitchcock and J. F. Nixon J. Organomet. Chem. 1992. 433 C11. N. Maigret L. Ricard C. Charrier. and F. Mathey Angew. Chem. Int. Ed. Engl. 1992 31 1031. N P As Sh and Bi subsequent reduction of the product gives a dianion which with (p-xylene),Fe2 + gives the first phosphorus analogue of ferrocenophane.' ' (q6-1.4-MezC&)FeCp+ (38) Scheme 1 12.5,3A5-Diphosphole derivatives result from (Ph,P)2CH and propargyl bromides while the 1A5,52.5-diphosphocin (39) results from the treatment of diphosphocanium dichloride with strong base. It was found to have a tub-like structure with two methallylic fragments connected through i5-phosphorus atoms which disrupt the total n-delocalization.' l4 Coupling BUT-P with diphenylketene at 100°C leads ultimately to the 1-phosphanaphthalene (40),while the 2-iodophosphinine o-complex of W(CO) can be functionalized at position 2.' The Ni(0) complex of phosphabenzene (ql-Ph 11.3 R.Bartsch A.Gelessus P. B. Hitchcock and J. F. Nixon. J. Oryunomer. Chem. 1992 430. C10; M. L. Sierra N. Maigret C. Charrier L. Ricard and F. Mathey Oryunometallics 1992 11 459. I I4 A. Schrnidpeter. J. Stocker and K. Karaghiosoff Chem. Ber. 1992 125 67; H. Schrnidbaur and S. F. Garnper. Orqanometallics 1992 11 986. 115 G. Markl A. Kallrnunzer H. Noth and K. Pohlrnann Tetrahedron Lett.1992,33 1597; H. T. Teunissen and F. Bickelhaupt ihrd. 1992 33 3537. D.A. Armitage C,H,P),Ni gives orange air-stable crystals with S symmetry and Ni-P bonds that are almost as short (212.7 pm) as those in the PF complex (210 to 21 1 pm).' l6 10 Nitrogen The protonation of dinitrogen has been reviewed along with nitrido complexes of transition metals.' ' Calculations regarding the stability of pentazole and its derivatives have been found to be consistent with the experimentally determined stabilizing effect of electron withdrawing substituents such as p-dimethylaminophenyl. Of the six isomers ofN considered calculations show the diazide to be the most stable with the Kekule and Dewar benzene/benzvalene forms being less stable.' l8 The nitridoferrate(I1) and cobaltate(1) anions FeN:- and CON; -,which result from the reductive thermolysis of Sr,N with Fe and Co respectively at 850"C possess triatomic linear structures.Heating Li/Ba with N in Ni crucibles gives a nitride with infinite Ni(N,) linear chains. Upon cooling a solution of barium and nitrogen in liquid sodium black needles of NaBa,N comprising face sharing Ba,N octahedra form. This subnitride provides an extension of alkali metal suboxide-like chemistry.' l9 Condensing Co,N(CO); with Co(CO) gives Co,N(CO):; which like its Rh analogue possesses a square-faced capped trigonal prism structure with nitrogen in the centre of the trigonal prism. Rh,N(CO), pyrolyses to the large cluster Rh,,N,(CO),,(p-CO)~~ which encloses two Rh and four N atoms with each nitrogen atom connected to five Rh atoms.'20 Cp:Sm(thf) cleaves the N-N bond of PhNHNHPh to give [CpfSm(NHPh),],.This also forms from reaction between [CpfSm(p-H)] and PhNH2.12' CpTiC1,NHBu' shows multiple-bond character in the Ti-N bond while Cp:Ta(=NPh)H has a Ta-N bond of length between that of double and triple.', The chloronitreno complex K(crown)WF,(=NCl) shows an almost linear W=NC1 group with a short W-N bond length of 172.4pm; NEEMo(OBu') is methylated by Me,Zn to give tetrameric [N~MoMe2(0Bu')~~(4-Bu'C,H,N)], with linear Mo=N-Mo bridges.' 23 NETcCl; gives cis-[TcN(Cl)L,] + PF (41) with chelating diphosphines and o-phen. With S,Cl, (41) L = o-phen gives the thionitrosyl cis-[Tc(NS)Cl(o-phen),] +PF .I2 Reacting CpK with TcI(NAr) gives q'-CpTc(NAr) .'2s '16 C.Elschenbroich M. Nowotny A. Behrendt. W. Massa and S. Wocadlo Angew. Chem. Inr. Ed. Engl. 1992 31 1343. 'I7 G. J. Leigh Acc. Chem. Res. 1992,25 177; K. Dehnicke and J. Strahle Angew. Chem.,Int. Ed. Engl. 1992 31 955. 1 I8 K. F. Ferris and R. J. Bartlett J. Am. Chem. Soc.. 1992 114. 8302; R. Engelke J. Phys. Chem. 1992 96 10 789. 'lYP. Hohn and R. Kniep Z. Narurforsch. Ted B 1992.47,477; 434; A. Gudat R. Kniep and A. Rabenau Z. Anorg. Ally. Chem. 1992,607,s; P. E. Rauch and A. Simon Angew. Chern. Int. Ed. Engl. 1992,31 1520. I20 G. Ciani N. Masciocchi A. Sironi A. Fumagalli and S. Martinengo Inorg. Chem. 1992 31 331; S. Martinengo G. Ciani. and A. Sironi. J. Chem. Soc.. Chem. Commun. 1992 1405. I21 W.J. Evans G. Kociok-Kohn V. S. Leong and J. W. Ziller Inorg. Chem. 1992 31. 3592. D. M. Giolando K. Kirschbaum L. J. Graves and U. Bolle Inory. Chem.. 1992 31 3887; G. Parkin A. van Asselt D. J. Leahy. L. Whinnery N.G. Hun R. W. Quan. L. M. Henling. W. P. Schaefer B.D. Santarsiero. and J. E. Bercaw Inorg. Chem.. 1992 31. 82. W. A. Herrmann S. Bogdanovic. J. Behm and M. Denk J. Orgunomet. Chem.. 1992,430 C33; H. Stenger K. Dehnicke. and W. Hiller Z. Nuturfbrsch.. Teil B 1992 47 1054. C. M. Archer J. R. Dilworth D. V. Griffiths. M. McPartlin and J. D. Kelly J. Chrm. SOL..,Dalton Trans. 1992 183; M. J. Clarke and J. Lu Inory. Chem. 1992 31. 2476; M. J. Clarke and J. Lu. J. Chem. Soc. Dalton Trans. 1992 1243. lZ5 A.K. Burrell and J.C. Bryan. Orgunomrtallics 1992 11 3501.N P As Sb and Bi The cis and trans isomers of W(N,),(PMe,Ph) have been separated.'26 1,2- Dimethylhydrazine was shown to complex as a four-electron donating diazene ligand to W(IV)(equation 10); the structure offuc-[(OC),(DPPE)W=NNMe,] shows the nitrogen ligand to bond as a Fischer carbene with an N-N bond length of 121 pm.',' ReOCl,( PPh,) gives a range of five- and six-coordinate bis(hydrazid0) complexes with MePhNNH, the hydrazide ligands being cis.' 28 -CH NMe Cp*WMei + MeNHNHMe -$-Cp*Me,W< I NMe Thermolysis of CpMo(NO)(CH,CMe,) gives the bimetallic neopentyl bridged complex CpMo(NO)(p-q'-q'-NO)(pCHCMe,)(CpMo=CHCMe,) in which one NO is terminal to one Mo atom and n-bonds to the other.'29 The structure of N,O supports a nitrosyl nitrite structure with a long N-N bond length of 189.1 pm (bond order 0.2) with N-0 being 112 pm long at the nitrosyl group and 121 pm long at the nitrite group.'30 11 Phosphorus-Nitrogen Compounds Phosphorus nitrides are described as the Cinderella of phosphorus chemistry.I3' Few molecules containing only phosphorus and nitrogen exist but recently the anions PNi-and P,N:g- were reported and the pyrolysis of ZnC1 with NH,Cl and (NPCI,) gives Zn,(P,,N2,)Cl containing the P 2N:$- anion which has a sodalite structure and a chloride ion encapsulated tetrahedrally by zinc ions.' 32 Ammonolysis of P,N gives HPN as a 3D framework of corner-sharing PN tetrahedra with hydrogen bonded to half of the nitrogen atoms.'33 The phosphatrane complexes XP(MeNCH,CH,),N [X = H + CS, MeS(S)C+ PhN=C(SMe)' Pt(iI) Hg(ir) or R~(I)]show a shortening of the bridge-head-bridgehead contact from 333 pm (Pt) to 196.7 pm (H' ) with a widening of the NPN angle from 104.5'-to 119.6 .I3 Calculations support a high degree of aromaticity for azaphospholes containing a2,j.3-phosphorus atoms but not for those containing a3,i3-phosphorus atoms.This applies to 1,3-aza2- 172,4-diaza- arid 1.2,3,4-trizazaphospholes. I 35 PrlNC-N under-goes [3 + 2lcycloaddition with CF3CH=N2 or MeO,CCH=N to give both the 1,2,3- and 1,2,4-diazaphospholes the structure of the latter suggesting n-delocalization T.A. George. J.R. D. DeBord. B. B. Kaul. C. J. Pickett. and D.J. Rose. Inorg. Chrm.. 1997. 31. 1295. T. E. Glassman M. G.Vale and R.R.Schrock.Inorg. Chem.. 1992.31. 1985 B. A. Arndtsen. T. K. Schoch. and L. McElwee-White. J. Am. Chem. Soc. 1992. 114. 7041. J. R. Dilworth. P. Jobanputra. S.J. Parrott R. M. Thompson D. C. Povey. and J. A. Zubieta. Polyhedron. 1592. 11. 147. P. Legzdins. S.J. Rettig. and J. E. Veltheer. J. Am. Chrm. Sot,. 1992. 114. 6922. ''" A. Simon. J. Horakh. A. Obermeyer and H. Borrmann. .4ngrw. Chcrn.. lnr. Ed. Engl.. 1992. 31. 301 13' O.J. Scherer Angew. Chem.. In[. Ed. Engl.. 1992. 31. 170. w. Schnick and J. Lucke. Angrw. Chrri.,In!. Ed. Engl.. 1992. 31. 213. 13' w. Schnick and J. Lucke. Z. Anorg. Ar'ly. Chem.. 1992. 610. 121. J. S.Tang M. A. H. Lararnay. V. Young. S. Ringrose. R. A. Jacobson. and J.G. Verkade .I Am. C~ICW. Soc. 1992. 114 3129.L. Nyulaszi. T. Veszpremi. J. Refly. B. Burkhardt. and M. RegItz. J. Am. Chem. So<,.. 1992. 114 9080. 70 D.A. Armitage with P-C bond lengths of 174 to 177 pm.' 36 1,3,5-Triaza-2,4-diphospha-penta-1,4-dienes Ar*N=PNRP=NAr* exist as S-type 'exo-endo' conformers in the solid and readily chelate to metal carbonyl residues through the two phosphorus atoms.13' Adding Ar*N-P+ to alkynes gives 2-A3-phosphachinolines (42) in which the P-N bond and P-C bonds are 163 and 175pm in length (equation ll).13* The Bu' R azadiphos-phane (Pr\N),PN reacts photochemically with bis(imin0)phosphoranes after N elimination to give diazaphosphetes e.g. (43) and (44) (equation 12).139 (44) (12) (43) Cyclodiphos-phazanes (RNPX) readily complex as monodentate ligands with metal carbonyl residues through P-coordination.40 12 Phosphorus and Arsenic MCl (M = P As Sb Bi) forms the chelated dichlorides 2,6-(Me,N),C6H,MC1 with Li[2,6-(Me,N),C6H,]. The Sb derivative has a distorted square pyramidal struc- ture.14' The preparation LiP(H)(2,4,6-Bu\C,H2) also gives [Li(2,4,6-Bu\C6H,)LiP(H)(2,4,6-Bu\C6H2)], an eight-membered ring with two two-coordi- nate Li atoms with short Li-C(ary1) o-bonds and two involving a Li-P o-bond and n-coordination with an aryl ring. 142 Coupling silylated phosphinoboranes with Pr',NBCl gives the trigonal bipyramidal P,(BNPr',),. The B-P analogue of the pentadienyl cations PhB(PMesBMes,), shows '36 J. Grobe D. Le Van M. Hegemann. B. Krebs and M. Lage Chem. Ber. 1992 125 411. 13' R.Detsch E. Niecke M. Nieger and F. Reichert. Chem. Ber. 1992 125 321. G. David E. Niecke and M. Nieger Terrahedron Lett. 1992 2335. 13' J. Boske E. Niecke B. Krebs M. Lage. and G. Henkel Chem. Ber. 1992. 125 2631. I4O M. S. Balakrishna and S.S. Krishnamurthy J. Orgunomet. Chem. 1992 424 243; V. S. Reddy S. S. Krishnamurthy and M. Nethaji ibid.,1992,438 99; T. K. Prakasha S. S. Krishnamurthy S. E. Davies M. F. Meidine and J. F. Nixon ihid. 1992 438 241. 14' D.A.Atwood A. H. Cowley and J. Ruiz Inorg. Chim.Acta 1992. 198 200 271. 142 S. Kurz and E. Hey-Hawkins Orgunometullics 1992. 11 2729. N P As Sb and Bi 71 dynamic behaviour in solution and B-P bond lengths of 186.4pm suggesting n-bonding. 143 The phosphides LiP[C(O)R] (R = cyclohexyl or adamantyl) on protonation give phosphines which show strong temperature-dependent keto-enol equilibria.The adamantyl derivatives crystallize from benzene as the enol tautomer with almost equal P-C bonds (180pm). The reaction of (dme)LiPH with HC0,Et gives dimeric HP=CHOLi as a mixture of E and 2 isomers whereas the reaction with (MeO),CO gives the methylidynephosphine (dme),LiOC-P with P-C 155.5 pm long and C-0 119.8pm 10ng.l~~ Coupling LiAsH with Bu'COCl gives LiAs(COBu') which reacts with acid to give the diarsine as the keto isomer.145 (Et,N),P reductively couples [Cl,PCH,] and CF,Br to give the trifluoromethyl substituted diphosphine; (Me,N),P adds para to pyrylium salts whereas they are ring opened by (Me,N),Sb (equation 13).'46 The diarsadigalletane [Bu'GaAsC~,H,(CH,NMe,),] results from (Bu'GaCI,) and Li,AsC,H,(CH,NMe,) in ether the structure showing amino coordination to each Ga atom in a Ga,As ring.14' (CF,),AsN has C,ssymmetry with azide trans to the CAsC bise~t0r.l~~ 13 Antimony and Bismuth A range of dithiolate complexes (L,Sb),CH and (LMe,Sb),O of Sb(II1) and Sb(v) has been made where L is R,NCS; ROCS; or (RO),PS .149 Ph,SbS,P(OPr') shows weak association (Sb ...S = 320 and 380 prn).l5' Sb(rr1) carboxylates Ar,SbOCOR are bridged polymers; chelated Sb(v) complexes R,SbL;+ have been made.151 Ph,Sb(oxalate) occurs as Ph4Sb+ Ph,Sb(oxalate); Bu'OOH oxidizes Ph,SbX (X = F or SCN) to the tetramer (Ph,SbXO), which has Ph,SbX,O units coupled to each Sb of an Sb,O four-membered ring.153 Two moles of hexafluorocumyl alcohol react with two moles of SbCl to give a 14' D.Dou. G. L. Wood E. Duesler R. T. Paine and H. Noth fnorg. Chem. 1992.31.3756; D. C. Pestana and P. P. Power Organometallics 1992 11 93. 144 G. Becker M. Schmidt W. Schwarz and M. Westerhausen Z. Anorg. Allg. Chem.. 1992 608 33; G. Becker W. Schwarz N. Seidler and M. Westerhausen ihid. 1992 612 72. 145 G. Becker M. Schmidt and M. Westerhausen Z. Anorg. Allg. Chem.. 1992 607. 101. 146 L. D. Field and M. P. Wilkinson Tetrahedron Lett. 1992 33 7601 ; Y. Madaule M. Ramarohetra and J.G. Wolf ibid.. 1992 33 1737. 14' D. A. Atwood A. H. Cowley R. A. Jones. and M. A. Mardones J. Orgunornet. Chern. 1992 439 C33. 14' H.G. Ang W. L. Kwik Y. W. Lee S. Liedle and H. Oberhammer J. Mol.Struct. 1992 268. 389. 149 S. Kraft and M. Wieber Z. Anorg. Ally. Chem. 1992 607 164. 153. lS0 C. Silvestru M. Curtui I. Haiduc M. J. Begley and D. B. Sowerby. J. Orgunornet. Chem. 1992,426 49. 15' P. Raj and A. K. Aggarwal Synth. React. fnorg. Met.-Org. Chem.. 1992 22 509 543. P. L. Millington and D. B. Sowerby J. Chem. Soc. Dalton Trans. 1992. 1199. I53 G. E. Forster. G. Southerington and D. B. Sowerby Phosphorus,Sulphur Silicon Rulut. Elern. 1992.64.55. D.A. Armitage 10-Sb-4-type antimonyate complex showing a distorted trigonal bipyramidal struc- ture and bismuth (111) with one hexafluorocumyl alcoxy group and an intramolecular coordinating o-aminomethylphenyl group show edge inversion at bismuth.' 54 Bis-muth(m) gives complexes bridged dimers with (CF,),CHO and C,F,O as the bridging groups; heating Ph,Bi under reflux with C,F,OH in thf gives the cluster [Bi,(p3- + 0,)(p3-OC,F,)]3 [Bi(OC6F5),],.2thf.' 55 Bi(OAc) reacts with iodine and alkenes in anhydrous acetic acid to give the iodoacetates but iodohydrins and ethers result if water is present.'56 Applying high-pressure 0 to Ag,O/Bi,O gives black crystals of Ag,,Bi,O,,.This change in oxidation state of Bi from (111) to (v) is the result of a pressure-induced shift of oxygen atoms delocalizing the 6s2 valence electrons.' 57 154 K. Akiba H. Nakata Y. Yamainoto and S. Kojima Chem.Lett. 1992,1559; Y. Yamamoto X. Chen and K. Akiba J. Am. Chem. SOC. 1992 114 7906. 155 C. M. Jones M. D. Burkart and K. H. Whitmire Angew. Chem. Int.Ed. Engl. 1992,31,451. C. M. Jones M. D. Burkart and K. H. Whitmire J. Chem. Soc. Chem. Commun.. 1992. 1638. 15' R. W. Trainor. G.B. Deacon W. R. Jackson and N. Giunta Ausr. J. Chrm. 1992. 45 265. 15' M. Bortz and M. Jansen Z. Anorg. Allg. Chem. 1992. 612 113.