Coordination Compounds of Coinage Metals with Vinylidenebis(diphenyl‐phosphane) and Its Disulfide and Their Reactivity towards Nucleophiles

Abstract

AbstractVinylidenebis(diphenylphosphane) reacts with gold(I) or gold(III) compounds to give dinuclear {[{Au(C6F5)]2[(PPh2)2CCH2{] or [Au{PPh2C(CH2)Ph2P)]2(ClO4)2] or mononuclear complexes ([Au(C6F5)3(PPh2C(CH2)Ph2P)]}, respectively. The latter reacts with gold(I) or silver(I) compounds to afford dinuclear [[Au(C6F5)3[PPh2C(CH2)Ph2P}AuX], XCl or C6F5) or trinuclear species {[{Au(C6F5)3{PPh2C(CH2)Ph2P{]2M]ClO4, MAu or Ag}. No addition of nucleophiles to the CC double bond is observed in these complexes, which contain the diphosphane acting as bridging or monodentate ligand. (SPPh2)2CCH2 reacts with AgClO4 to give [Ag{SPPh2C(CH2)Ph2PS}]2‐(ClO4)2or[Ag[PPh2C(CH2)Ph2P]2]ClO4. The crystal structure of [Au(C6F5)3{PPh2C(CH2)Ph2P}Au(C6F5)] has been established by X‐ray crystallography, and confirms the expected square planar and linear geometry for the Au111 and Au1 centres, respectively.