Architecture and properties of platinum group metal cluster complexes bearing polydentate ligands

Reaction of diplatinum complexes 1 bearing bis(diphenylphosphinomethyl)phenylphosphine （dpmp）[Pt - D22 - D2(dpmp) - D22 - D2(RNC) - D22 - D2] - D12+ - D1 with M(RNC) - D22 - D2(M = Pt or Pd) underwentinsertion of the metal fragment into a Pt-Pt bond to give homo- or heterotrinuclear a -framecomplexes [Pt - D22 - D2MX(dpmp) - D22 - D2(RNC) - D24 - D2] - D12+ - D1. When complex 1 was treated withgroup 11 metal ions，the metal ions incorporated into a diplatinum center to give[Pt - D22 - D2M(dpmp) - D22 - D2(RNC) - D22 - D2] - D13+ - D1 (M = Au, AuAg) or [Pt - D22 - D2MX(dpmp) - D22 - D2(RNC) - D22 - D2] - D12+ - D1 (M = Cu；X = Cl, Br，I) (Scheme 1). In the - D131 - D1P{- D11 - D1H} nmr spectra of Pt-Cu mixed complexes the chemicalshifts与halogens. Trinuclear complex相关[Pt - D23 - D2(dpmp) - D22 - D2(RNC) - D24 - D2] - D12+ - D1 reacted readily with [NO][BF - D24 - D2] to yieldunprecedented nitrosyl-bridged double A-frame complexes[Pt - D23 - D2(dpmp) - D22 - D2(NO)(RNC) - D22 - D2] - D14+ - D1. Dinuclear palladium complexes，[Pd - D22 - D2(dppf) - D22 - D2(RNC) - D22 - D2] - D12+ - D1 were prepared from the reaction of[Pd - D22 - D2(RNC) - D24 - D2] - D12+ - D1 with 1，1'-bis(diphenylphosphino)ferrocene (dppf). The photochemical reactions of these complexes led tocleavage of a Pd-Pd bond.Our research on platinum and palladium complexes bearing triphosphine have前报告：Trends in Organometallic Chemistry， 35-69（1999）。

Reaction of diplatinum complexes 1 bearing bis(diphenylphosphinomethyl)phenylphosphine (dpmp), [PtィイD22ィエD2(dpmp)ィイD22ィエD2(RNC)ィイD22ィエD2]ィイD12+ィエD1 with M(RNC)ィイD22ィエD2 (M = Pt or Pd) underwent insertion of the metal fragment into a Pt-Pt bond to give homo- or heterotrinuclear A-frame complexes [PtィイD22ィエD2MX(dpmp)ィイD22ィエD2(RNC)ィイD24ィエD2]ィイD12+ィエD1. When complex 1 was treated with group 11 metal ions, the metal ions were incorporated into a diplatinum center to give [PtィイD22ィエD2M(dpmp)ィイD22ィエD2(RNC)ィイD22ィエD2]ィイD13+ィエD1 (M = Au, Ag) or [PtィイD22ィエD2MX(dpmp)ィイD22ィエD2(RNC)ィイD22ィエD2]ィイD12+ィエD1 (M = Cu ; X = Cl, Br, I) (Scheme 1). In the ィイD131ィエD1P{ィイD11ィエD1H} nmr spectra of Pt-Cu mixed complexes the chemical shifts was related with halogens. Trinuclear complex [PtィイD23ィエD2(dpmp)ィイD22ィエD2(RNC)ィイD24ィエD2]ィイD12+ィエD1 reacted readily with [NO][BFィイD24ィエD2] to yield unprecedented nitrosyl-bridged double A-frame complexes, [PtィイD23ィエD2(dpmp)ィイD22ィエD2(NO)(RNC)ィイD22ィエD2]ィイD14+ィエD1. Dinuclear palladium complexes, [PdィイD22ィエD2(dppf)ィイD22ィエD2(RNC)ィイD22ィエD2]ィイD12+ィエD1 were prepared from the reaction of [PdィイD22ィエD2(RNC)ィイD24ィエD2]ィイD12+ィエD1 with 1, 1'-bis(diphenylphosphino)ferrocene (dppf). The photochemical reactions of these complexes led to cleavage of a Pd-Pd bond.Our research on platinum and palladium complexes bearing triphosphine have been reported : Trends in Organometallic Chemistry, 35-69 (1999).