Stanley Bruce Wild

Synthesis of o-phenylenebis(dimethylstibine) and some derivatives of divalent nickel, palladium, and platinum and of zerovalent chromium, molybdenum, and tungsten

Abstract The ditertiary distibine o -phenylenebis(dimethylstibine) ( distib ) has been prepared in 9% yield from the reaction between sodium dimethylstibide and o -bromoiodobenzene in liquid ammonia. The distibine readily forms the square-planar complexes [MX 2 (distib)] (where M = Pd or Pt and X = Cl, Br, I, or SCN) and the five co-ordinate diamagnetic complex [NiCl(distib) 2 ]Cl. UV irradiation of solutions of chromium, molybdenum, and tungsten hexacarbonyls in tetrahydrofuran with the ligand affords the expected octahedral complexes [M(CO) 4 (distib)] (where M = Cr,Mo, or W). A weaker Ligand field strength of the ditertiary distibine compared with the analogous ditertiary diaraine is indicated by a comparison of the electronic spectra of the Pd II and Ni II complexes of both ligands.

Organostibines as ligands. Synthesis of dimethyl(α-picolyl)stibine, dimethyl(8-quinolyl)stibine, and (R;S)-methylphenyl(8-quinolyl)stibine and some transition metal derivatives

Abstract The unsymmetrical mono-tertiary stibines dimethyl(α-picolyl)stibine (picstib), dimethyl(8-quinolyl)stibine (quinstib), and ( R ; S )-methylphenyl(8-quinolyl)stibine ( R ; S -quinstib) have been synthesised and the square-planar complexes [MX 2 (picstib)], [MX 2 (quinstib)] (where M = Pd or Pt and X = Cl, Br, I or SCN) and [MCl 2 ( R ; S -quinstib)] (where M = Pd or Pt) isolated. The thiocyanato derivatives display linkage isomerism. The octahedral complexes [M(CO) 4- (picstib)] and [M(CO) 4 (quinstib)] have also been prepared from the metal hexacarbonyls and the appropriate ligands by UV irradiation in tetrahydrofuran.

Gas phase molecular anion formation by η4- and η6-cycloheptatriene derivatives of zerovalent iron, chromiun, molybdenum, and tungsten tricarbonyls

Abstract The title compounds form molecular anions in high abundance in their negative ion mass spectra in apparent violation of the rare-gas rule.

Synthesis of o-phenylenebis(dimethylstibine) and some transition metal derivatives

Abstract The new chelating agent o-phenylenebis(dimethylstibine) has been synthesised and shown to form the expected palladium(II) and platinum(II) complexes.

Gas phase electron attachment reactions with organometallic compounds; molecular anion formation and negative ion mass spectra of a series of η4-dienetricarbonyliron compounds

Electron attachment by secondary electron capture in the gas phase with a series of conjugated η4-dienetricarbonyliron compounds yields molecular anions which decompose by CO and diene eliminations; however, η4-cyclobutadienetricarbonyliron, which under-goes dissociative electron capture to give the [M– CO][graphic omitted] ion at the highest m/e in its negative ion mass spectrum, decomposes only by elimination of CO ligands.

Synthesis, separation into diastereoisomers, and resolution of o-phenylenebis(methylphenylarsine) and related studies of the o-phenylenediarsine moiety

The nucleophilic substitution of o-dichlorobenzene by sodium methylphenylarsenide is described. The principal products of the reaction are meso- and racemic-o-phenylenebis(methylphenylarsine), although small quantities of the following compounds are formed as side-products: dimethylphenylarsine; ethoxymethylphenylarsine; methyldiphenylarsine; 1-chloro-2-methylphenylarsinobenzene; methylphenylarsinic acid; 1,2-dimethyl-1,2-diphenyldiarsane; 1,3-dimethyl-1,2,3-triphenyltriarsane; and 5,10-dihydro-5,10-diphenylarsanthren. A study of the possible stereospecific synthesis of racemic-o-phenylenebis(methylphenylarsine) from certain o-phenylenediarsine derivatives is described. The solid-state elimination of bromomethane from o-phenylenebis(dibromodimethylarsine) is stereospecific. The two diastereoisomers of o-phenylenebis(methylphenylarsine) have been separated and identified by means of their fac-[PtMe3(I)(diarsine)] complexes using 1H n.m.r. spectroscopy and the racemic-diarsine subsequently resolved via its D(–)-dibenzoylhydrogentartrate salt.

Stereochemistry of seven-co-ordination: crystal structures of rac- and meso-tricarbonyldi-iodo[o-phenylenebis(methylphenylarsine)]molybdenum(II)

The crystal structures of the title compounds (I)[rac–o–C6H4(AsMePh)2Mo(CO)3l2], CHCl3, and (II)[meso-o-C6H4(AsMePh)2Mo(CO)3l2], have been determined from diffractometer data by the heavy-atom method and refined by least squares to R 0·08 [(I), 2809 reflections] and 0·11 [(II) 2371 reflections]. Crystals of both compounds are triclinic, space group P, with Z= 2 in unit cells of dimensions : (I), a= 14·985(5), b= 12·337(3), c= 9·654(1)A, α= 110·78(2), β= 101·90(2), γ= 104·74(2)°; (II), a= 15·828(6), b= 10·505(1), c= 9·733(1)A, α= 120·604(8), β= 98·99(2), γ= 97·69(2)°. Both complexes are comprised of discrete molecules with seven-co-ordinate molybdenum atoms, being of the type [M(bidentate)(unidentate)5]. A theoretical description of this system has been developed in terms of repulsion theory, yielding four different possible stereochemical types of which examples are found for three among these and previously determined structures of this type.

Partial asymmetric synthesis of substituted trans-2,3-diaryloxirans using optically active arsonium ylides

Ylides derived from optically active arsonium salts react with aromatic aldehydes to give trans-2,3-diaryl-oxirans in high chemical yields and with optical purities of between 4·7 and 38%.

Crystal structure of tetraphenylarsonium cis-tetracarbonyl(chloromercurio)(dichloromercurio)ferrate

The crystal structure of the title compound has been determined by X-ray diffraction (heavy-atom) methods and refined by least squares to R 0.059 for 2 917 observed reflections. Crystals are triclinic P, a = 11.848(3), b= 13.524(4), c= 11.624(3)A, α= 123.87(2), β= 94.01 (2), γ= 90.91 (2)°, Z= 2. Within the anion, the two mercury atoms are bonded cis in the co-ordination sphere of the six-co-ordinate iron atom [Fe–Hg 2.560(3) and 2.516(4)A, Hg–Fe–Hg 80.3(1)°]. The anion lies close to a centre of symmetry and is linked to its inversion image by one of the chlorine atoms. The reduction in the Hg–Fe–Hg angle from the regular octahedral value is shown to be a consequence of the more extended Fe–Hg relative to the Fe–CO bonds, rather than to Hg ⋯ Hg interactions.