From diphosphane to diphosphodiide gold(III) derivatives of 1,2-diphosphinobenzene

Treatment of 1,2-diphosphinobenzene with Au(C6F5)3(tht)] leads to the diphosphane derivative {Au(C6F5)3}(1,2-PH2C6H4PH2)] (1), which further reacts with other pentafluorophenylgold(III) reagents in the presence of acetylacetonate as deprotonating agent to afford phosphane-phosphide complexes. The noncyclic PPN{Au(C6F5)3}2(1,2-PHC6H4PH2)] (2; PPN = bis(triphenylphosphine)iminium) has been shown to be a useful starting material for the synthesis of higher nuclearity cyclic or noncyclic diphosphide or even diphosphodiide derivatives through similar reactions. The crystal structures of the trinuclear anionic NBu4{Au(C6F5)3}(1,2-PHC6H4PH){Au(C6F5)2Cl}{mu-Au(C6F5)2}] (3) and the hexanuclear {Au(C6F5)3}(1,2-PC6H4P){Au(C6F5)3}{mu-M(dppe)M}2] (M = Au (12), Ag (13)) have been established by X-ray diffraction methods, the last complexes having a bicyclic ring containing three intramolecular interactions between the M(I) centres.