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