TRIS(DIPHENYLPHOSPHINO)METHANIDE GOLD(III) COMPLEXES - CRYSTAL-STRUCTURES OF [AU(C6F5)(2)((PH(2)P)(2)CPPH2)] AND [(F5C6)(2)AU((PH(2)P)(2)CPPH(2))AUCL]

The reaction of [Au(C6F5)(2)(acac)] (acac = acetylacetonate) with (Ph(2)P)(3)CH led to [Au(C6F5)(2)- {(Ph(2)P)(2)CPPh(2)}] 1, which reacts further with [AuX(tht)] (X = Cl or C6F5, tht = tetrahydrothiophene), [Au(tht)2]ClO4 or AgClO4 to give dinuclear [(F5C6)(2)Au{(Ph(2)P)(2)CPPh(2)}AuX] or trinuclear complexes [{Au(C6F5)(2)[(Ph(2)P)(2)CPPh(2)]}(2)M] (M = Au or Ag). Complex 1 reacted with gold(III) complexes to give dinuclear [(F5C6)(2)Au{(Ph(2)P)(2)CPPh(2))Au(C6F5)(2)X] (X = Cl or C6F5) or trinuclear complexes [{Au-(C6F5)(2)[(Ph(2)P)(2)CPPh(2)]}Au-2(C6F5)(2)]. Complex 1 is protonated by reaction with HBF4. The structures of complex 1 and [(F5C6)(2)Au((Ph(2)P)(2)CPPh(2)}AuCl] have been established by X-ray crystallography, confirming in the latter that the gold(I) centre is co-ordinated to the free phosphorus instead of the methanide C.