From Diphosphane to Diphosphodiide Gold( III ) Derivatives of 1,2‐Diphosphinobenzene

Treatment of 1,2‐diphosphinobenzene with [Au(C 6 F 5 ) 3 (tht)] leads to the diphosphane derivative [{Au(C 6 F 5 ) 3 }(1,2‐PH 2 C 6 H 4 PH 2 )] ( 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(C 6 F 5 ) 3 } 2 (1,2‐PHC 6 H 4 PH 2 )] ( 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 NBu 4 [{Au(C 6 F 5 ) 3 }(1,2‐PHC 6 H 4 PH){Au(C 6 F 5 ) 2 Cl}{μ‐Au(C 6 F 5 ) 2 }] ( 3 ) and the hexanuclear [{Au(C 6 F 5 ) 3 }(1,2‐PC 6 H 4 P){Au(C 6 F 5 ) 3 }{μ‐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.