http://users.auth.gr/akrivos/metaptyxiaka/proxorimeni anorgani/coord_chem_rev_199_2000_89.pdf

The preparation and coordination chemistry of phosphorussulfur donor ligands

Rhodium(I) phosphine complexes containing bidentate unsaturated thio ligands

The complexes [Zr(cp)2(PR2)X](cp =η-C5H5; R = SiMe3; X = Cl, 2; PR2, 3; or Me, 6) and [Zr(η-C5H4R)2(PR2)Y](Y = Cl, 4; or PR2, 5) were obtained from [{Li(µ-PR2)(thf)2}2]1(thf = tetrahydrofuran) and [Zr(cp)2Cl2] or [Zr(η-C5H4R)2Cl2], respectively. Each of 2, 3, and 6 was treated with a variety of reagents causing scission of the Zr–P bond. Two types of reactions were observed: (i) substitution or (ii) insertion. Examples of (i) are the reaction of (a) complex 3 with Mel to afford [Zr(cp)2I(PR2)]7, (b)2 with LiOR′(R′= C6H2But2-2,6-Me-4), SiMe3(N3), Mel or EtOH yielding [Zr(cp)2Cl(Z)](Z = OR′, 8; N3, 9; or I, 10) or [{Zr(cp)2Cl}2(µ-O)]11, respectively and (c)2 with (AlMe3)2 to furnish [AlMe2(µ-PR2)]212. The X-ray structure of 12 shows a planar nearly square Al2P2 ring [Al–P 2.460(2) and 2.453(2)A, P–Al–P′89.4(1), Al–P–Al′ 90.60(5)°], a configuration which is retained in hydrocarbon solution (1H and 29Si NMR spectroscopy). Type (ii) reactions were those between (a)2 and a diazoalkane N2CR′R″ yielding [[graphic omitted](PR2)}](R′= R″= Ph, 13; or R′= H, R″= CO2Et, 14), (b)2 or 6 with CS2, affording [Zr(cp)2{S2C(PR2)}X](X = Cl, 15; or Me, 16), and (c)3 with white phosphorus to give [[graphic omitted]]17. Each of the complexes 3 and 6 reacted with sulphur to furnish [{Zr(cp)2(µ-S)}2], which was also obtained by thermolysis of 15. The thermolysis of 2, 4 or 6 led to elimination of SiMe3X (X = Cl or Me).

Bis(trimethylsilyl)phosphido complexes. Part 3. Syntheses, structures and reactions of [bis(trimethylsilyl)phosphido]-zirconocene(IV) complexes and the X-ray structure of {AlMe2[µ-P(SiMe3)2]}2

The electrochemical oxidation of a number of metals in acetonitrile solutions of PPh2H gives rise to M(PPh2)n compounds (M = Co, Zn or Cd, n= 2; M = Cu, Ag or Au, n= 1). With anodic nickel the product is Ni(PPh2)·PPh2H. In the presence of elemental sulphur such oxidation reactions yield [M(S2PPh2)2](M = Co, Zn or Cd). The electrochemical processes involved have been identified. The crystal structure of the addition compound [Cu4(PPh2)4(dppm)2]·4MeCN 1[dppm = bis(diphenylphosphino)methane] has been determined by X-ray crystallography, which reveals a Cu4P4 ring, capped by Cu2PCP'2 rings. Crystal parameters: triclinic, space group P, a= 14.719(4), b= 13.649(5), c= 17.112(5)A, α= 112.40(3), β= 106.22(2), γ= 115.39(2)° and Z= 1; R= 0.0632 for 3622 observed reflections [I 3σ(I)]. The compound Ni(PPh2)·PPh2H is oxidized by elemental oxygen, sulphur or selenium to give [Ni(E2PPh2)2](E = O, S or Se), and also reacts with PhNCS to yield [Ni{PPh2(SCNPh)}2]2. Crystal parameters: triclinic, space group P, a= 8.950(6), b= 9.745(4), c= 10.366(7)A,α= 112.28(4), β= 99.09(5), γ= 90.88(4)° and Z= 1. Disorder prevented this structure from being refined beyond R= 0.1612, but the essential features of the square-planar NiS2P2 core were identified. The crystal parameters of [Ni(O2PPh2)2(HO2PPh2)2(MeCN)2]3 are monoclinic, space group P21/c, a= 12.420(5), b= 9.737(7), c= 20.729(16)A, β= 100.29(5)° and Z= 2. The nickel atom is co-ordinated by two monodentate Ph2PO(O)– ligands and two monodentate Ph2(O)OH ligands which are hydrogen-bonded to their anionic analogues, and by two MeCN molecules, to give a NiO2O′2N2 core.

Direct electrochemical synthesis and crystallographic characterization of metal diphenylphosphido and diphenylthiophosphinato compounds, and some derivatives

Sigurjon N. Olafsson

Papers

Bis(diorganylphosphinodithioformiato‐S,P)nickel(II)‐Komplexe – neuartige Vierring‐Chelate

Bis(diorganylphosphinodithioformato‐S,P)nickel(II)Complexes—Novel Four‐Membered Ring Chelates