Coordination compounds of coinage metals with vinylidenebis(diphenylphosphane) and its disulfide and their reactivity towards nucleophiles

Vinylidenebis(diphenylphosphane) reacts with gold(I) or gold(III) compounds to give dinuclear {[{(Au(C6F5)}(2){(PPh2)(2)C=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}}(2)M]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)(2)C=CH2 reacts with AgClO4 to give [Ag{SPPh2C(=CH2)Ph2PS}](2)(ClO4)(2) or [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 Au-III and Au-I centres, respectively.