AbstractDie sechs‐, fünf‐ und vierfach‐koordinierten Ni(II)‐Komplexe (I), (II) und (III) entstehen bei der 2:1‐molaren Umsetzung des Titelliganden mit entsprechenden Ni‐Salzen in heißem Äthanol.

The molecular structure of 10-phenylphenoxaphosphine has been determined by X-ray diffraction (heavy-atom) methods. The unit cell is monoclinic, a= 8.47(1), b= 9.48(1), c= 19.83(1)Å, γ= 118.85(2)°, space group P21/a, Z= 4. Diffractometer data were refined to R 0.054 for 2 159 observed reflections. The phenoxaphosphine residue is folded about a line almost passing through the oxygen and phosphorus atoms, and the geometry at the phosphorus atom is nonplanar.

Chemischer InformationsdienstVolume 4, Issue 7 Organoelement Compounds ChemInform Abstract: KONSTIT. DER ADDUKTE AUS TERT. PHOSPHINOXIDEN UND ARENSULFONAMIDEN DAVID W. ALLEN, DAVID W. ALLENSearch for more papers by this authorFREDERICK G. MANN, FREDERICK G. MANNSearch for more papers by this authorJOHN C. TEBBY, JOHN C. TEBBYSearch for more papers by this author DAVID W. ALLEN, DAVID W. ALLENSearch for more papers by this authorFREDERICK G. MANN, FREDERICK G. MANNSearch for more papers by this authorJOHN C. TEBBY, JOHN C. TEBBYSearch for more papers by this author First published: February 13, 1973 https://doi.org/10.1002/chin.197307335AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume4, Issue7February 13, 1973 RelatedInformation

AbstractDie Einflüsse sterischer und elektronischer Eigenschaften von einzähnigen, heterocyclischen, tert. Phosphinen auf ihre Fähigkeit, fünffach‐koordinierte Tris‐[phosphin]‐Komplexe zu bilden, wird untersucht.

Evidence that tertiary phosphine oxides and arenesulphonamides combine in a 1 : 1 molecular ratio to form strongly hydrogen-bonded adducts, which do not dissociate in chloroform solution, is obtained from molecular weight, conductance, 1H and 31P n.m.r., and i.r. spectral measurements. Tertiary phosphines and anhydrous Chloramine-T give phosphine imides, which in the presence of water are hydrolysed to give the corresponding phosphine oxides and toluene-p-sulphonamide. Evidence is adduced supporting the six-membered, hydrogen-bonded, cyclic structure (VIII) for these adducts.

The effects of variation in the steric and electronic properties of a number of heterocyclic unidentate tertiary phosphine ligands on their ability to form five-co-ordinate tris(phosphine) complexes with nickel(II), palladium(II), and platinum(II) dihalides, have been studied.In contrast to 5-methyl- and 5-ethyl-5H-dibenzophosphole (I; R = Me, Et) which give rise to a series of five-co-ordinate complexes with the above halides, both 5-isopropyl- and 5-t-butyl-5H-dibenzophosphole (I; R = Pri, But) form only four-co-ordinate complexes of type (phos)2MX2. The nickel(II) dihalide complexes of this type have a tetrahedral structure, indicated by their magnetic and spectroscopic properties. 1H N.m.r. studies show that in solution in deuteriochloroform, the four-co-ordinate PdIIBr2 complexes of both the phosphines (I; R = Pri) and (I; R = But) have the trans-configuration and the PtIICl2 complex of (I; R = But) also has this configuration, whereas the PtIICl2 complex of (I; R = Pri) has the cis-configuration.2,8-Dimethoxy-5-phenyl-5H-dibenzophosphole (II) resembles 5-phenyl-5H-dibenzophosphole (I; R = Ph) in forming four-co-ordinate, tetrahedral, nickel(II) dihalide complexes.10-Methyl-10-phenoxaphosphine (IV; R = Me) forms five-co-ordinate tris(phosphine)MX2 complexes with NiIICl2, PdIIBr2, and PtIICl2. 10-Ethyl-10-phenoxaphosphine (IV; R = Et) forms five-co-ordinate complexes apparently only with NiIIBr2 and NiIIl2, four-co-ordinate species being formed with NiIICl2 and NiII(NCS)2 and also with PdIIBr2 and PtIICl2. 10-Phenyl-10-phenoxaphosphine (IV; R = Ph) forms only four-co-ordinate complexes with nickel salts.The seven-membered cyclic triarylphosphine, 10,11-dihydro-5-phenyl-5H-dibenzo[b,f]phosphepin (V) is unusual in forming diamagnetic, square-planar, nickel(II) dihalide complexes.

The property of the above diamines to act as chelating agents, forming stable five-membered ring systems with PdCl2, PdBr2, PtCl2, and IrCl2, and similar but less-stable systems with CdII and CuII have been recorded. The compounds with PtCl2 are very readily formed from hexachloroplatinic(IV) acid, but the compounds from K2[IrCl6] were very slowly formed with much reduction to the metal.It is now shown beyond doubt that the supposed iridium compounds were in fact platinum compounds, formed from platinum(IV) chloride present as an impurity in the iridium(IV) chloride employed.

The 1 : 1 complexes of the chelating diphosphine, 2,2′-biphenylylenebisdiethylphosphine, with nickel(II) halides and thiocyanate and with palladium(II) bromide have been prepared, and their magnetic properties and electronic and n.m.r. spectra studied.

The 9-alkyl-9-phosphafluorenes (I), alternatively named 5-alkyl-5H-dibenzophospholes (Ia; R = Me, Et), form a series of five-co-ordinate complexes of the type phos3 MX2(M = NiII, X = Cl, Br, I, NCS, CN; M = PdII, X = Br; M = Pt,II X = Br, SCN; M = CoII, X = Br), which are stable in the solid state but which undergo reversible dissociation in solution in certain organic solvents. The magnetic and spectroscopic properties of the complexes are discussed and related to those of other five-co-ordinate complexes of the above metals. The nickel(II) complexes are unusual in having magnetic moments in the range from 0·65–1·5 B.M., whereas the corresponding cobalt(II) complexes are of the normal low-spin type, having moments of 1·95 B.M.Evidence for the structure of dicyanotris(9-methyl-9-phosphafluorene)nickel(II) has been adduced by X-ray crystallographic analysis.Four-co-ordinate complexes of the above ligands with palladium(II) and platinum(II) halides and cyanides have also been prepared, and their structures in solution examined by 1H n.m.r. spectroscopy. The complex phos2 PtCl2(phos = 9-methyl-9-phosphafluorene) has the cis-configuration in trifluoroacetic acid solution, whereas the corresponding platinum and palladium cyanide complexes have the trans-configuration.9-Phenyl-9-phosphafluorene (I; R = Ph) resembles triphenylphosphine in forming only normal four-co-ordinate complexes with the above metal halides.It is suggested that unusual co-ordinating ability of the 9-alkyl-9-phosphafluorenes [and of 2-phenylisophosphindoline (III) which also forms a similar series of complexes] is due to a favourable combination of both steric and electronic (donor–acceptor) properties.Preliminary experiments show that 10-methylphenoxaphosphine (VI; R = Me) also forms similar five-co-ordinate complexes, but the 10-phenyl analogue forms only four-co-ordinate complexes.

Dicyanotris-(9-methyl-9-phosphafluorene)nickel(II) and dicyanotris-(9-ethyl-9-phosphafluorene)nickel(II) have tetragonal pyramidal and trigonal bipyramidal configurations, respectively, in the solid state, though in solution they have the same structure.

The synthesis of the above diphosphine is described. It forms cyclic diquaternary dibromides by union with the alkylene dibromides, Br·[CH2]n·Br, where n= 1–4, and a similar salt with o-xylylene dibromide. These salts, and the dimethiodide of the diphosphine, when heated, undergo a novel degradation to give 9-alkyl-9-phosphafluorenes. These reactions are compared with those shown by the analogous cyclic tetramethyl diarsonium dibromides, in which the dibromides formed from Br·[CH2]n·Br where n= 2–4 undergo a similar degradation to give the 9-alkyl-9-arsafluorenes, but the other members lose alkyl bromide with retention of the heterocyclic ring as a ditertiary arsine. The strictly analogous tetraethyl diarsonium dibromides undergo thermal decomposition with degradation of the heterocyclic ring. It is suggested that the ring contraction reactions shown by all these series of salts when heated are examples of a general internal nucleophilic displacement mechanism; other examples of this are discussed.Alkaline hydrolysis of certain of the above heterocyclic phosphonium salts occurs with ring-opening to give phosphine oxides.

Phenyldilithiophosphine can be prepared in tetrahydrofuran by the action of lithium on phenylphosphonous dichloride and (more satisfactorily) by that of butyl-lithium on phenylphosphine. It reacts with o-bromoiodobenezene and with o-di-iodobenzene to give the crystalline 1,2,3-triphenyl-1,2,3-triphosphaindane, 5,10-dihydro-5,10-diphenylphosphanthren [isolated as the insoluble di(benzyl bromide)], and much apparently polymeric material. The structure of the triphosphaindane has been elucidated by chemical means, and independently by X-ray crystal analysis. A mechanism for the formation of the triphosphaindane and the dihydrophosphanthren, involving the interaction of benzyne and (PhP)n units, is suggested.Triphenyltriphosphaindane forms a monosulphide and two isomeric disulphides but not, apparently, a trisulphide, whereas the corresponding triethyl compound readily forms a trisulphide. The structure of the two disulphides can be deduced from the configuration of the parent phosphaindane.The yield of the diphenylphosphanthren di(benzyl bromide) by the present method is lower than that by the earlier recorded method but the present method is more rapid.