Zero-valent group 10 metal complexes with a triphosphine ligand, [M(dpmp) 2], where MPt, Pd, Ni, and dpmp = bis(diphenylphosphinomethyl)phenylphosphine

Abstract

Reduction of [MCl 2(dpmp)] by NaBH 4 in the presence of dpmp afforded zero-valent mononuclear complexes, [M(dpmp) 2], in good yields (41–86%), where MPt ( 4), Pd ( 5), Ni ( 6), and dpmp = bis(diphenylphosphinomethyl)phenylphosphine. The nickell ( II) starting complex, [NiCl 2(dpmp)] ( 3), was prepared by the reaction of NiCl 2·6H 2O with dpmp and was characterized by X-ray crystallography to be isomorphous with [PdCl 2(dpmp)] ( 2) ( 3·CH 2Cl 2: monoclinic, P2 1/c, a = 10.886(4), b = 21.867(5), c = 13.786(4) A ̊ , V = 3265 A ̊ 3, Z = 4, R = 0.071 and R w = 0.062) . Th 31P( 1H) NMR spectra of 4–6 were similar to each other showing three multiplets. The structure of 4 was shown by X-ray analysis to have a mononuclear Pt atom tetrahedrally coordinated by two dpmp ligands through four terminal phosphorus atoms ( 4·4 C 6 H 6: monoclinic, P2/c, a = 13.563(8), b = 17.098(7), c = 16.995(7) A ̊ , V = 3774 A. Z = 2, R = 0.007 and R w = 0.059 ). The central P atom of dpmp was uncoordinated. Reaction of 4 with [Pt(XyINC) 4](PF 6) 2 (XyINC = 2.6-xylyl isocyanide) gave a mixture of isomteric diplatinum complexes, syn- and anti-[Pt 2(dpmp) 2(XyINC) 2](PF 6) 2 ( syn-7 and anti-7).