Heteropolynuclear phosphide complexes: phosphorus as unique atom bridging coinage metal centres

In this paper we describe the synthesis and reactivity of the diphenylphosphine derivatives Au(C6F5)(PPh2H)] and trans-Au(C6F5)2(PPh2H)2]ClO4. Reactions of the latter or the neutral Au(C6F5)3(PPh2H)] with the appropriate Group 11 metal reagents (M = Au, Ag, Cu) in the presence of acetylacetonate afford a series of novel Au(III)-M phosphido-bridged complexes, which have been scarcely represented to date. The crystal structure of the tetranuclear (Au(C6F5)2(mu-PPh2)2Ag)2] and the dinuclear Au(C6F5)3(mu-PPh2)M(PPh3)] (M = Au,Ag) complexes were established by X-ray diffraction methods. The synthesis and deprotonating activity of the anionic gold(III) complex PPNAu(C6F5)3(acac)] (PNN = N(PPh3)2]+) was studied.