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

Diplatin复合体的反应1个轴承之二（diphenylphosphinomethyl）phenylphosphine （dpmp），[Pt型D22型D2（dpmp）型D22型D2（RNC）型D2]型D12+型D1 with M（RNC）型D22型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-D22-D2MX（dpmp）-D22-D2（RNC）イイD24イエD2]イイD12+イエD1。When complex 1 was treated with group 11 metal ions， the metal ions were incorporated into a diplatinum center to give [PtイイD22エD2M（dpmp）イD22エD2（RNC）イD13+イD1（M = Au， Ag） or [PtイルD22イルD2MX（dpmp）イルD22イルD2（RNC）イルD12+イルD1 （M = Cu ; X = Cl， Br， I） （Scheme 1）。在D131中D1P{D11中D1H} nmr spectra of Pt-Cu mixed complexes the chemical shifts was related with halogens。Trinuclear complex [PtイルD23イルD2（dpmp）イルD22イルD2（RNC）イルD12+イルD1 reacted readily with [NO][BFイルD24イルD2] to yield unprecedented nitrosyl-bridged double A-frame complexes， [PtイルD23イルD2（Dpmp）イルD2（NO）（RNC）イルD22イルD2）イルD14+イルD1. Dinuclear palladium complexes， [Pd ― D22 ― D2（dppf）― D22 ― D2（RNC）― D12+ ― D1 were prepared from the reaction of [Pd ― D22 ― D2（RNC）― D24 ― D2] ― D12+ ― D1 with 1， 1'-bis（diphenylphosphino）ferrocene （dppf）。这些复合体的光化学反应导致了清除Pd-Pd键的作用，我们关于已经报告过的铂和钯复合体持有三磷酸酶的研究：有机化学趋势， 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).