DINUCLEAR, TRINUCLEAR AND TETRA-NUCLEAR GOLD(I) COMPLEXES WITH TRIS(DIPHENYLPHOSPHINO)-METHANE OR TRIS(DIPHENYLPHOSPHINO)-METHANIDE AS LIGAND - CRYSTAL-STRUCTURES OF 2 MODIFICATIONS OF ](O)PH2PC(PPH2AUPPH2)2CPPH2(O)]CENTER-DOT-4CH2CL2

The reaction of [Au(tht)2]ClO4 or [Au(acac)(PPh3)] (tht = tetrahydrothiophene, acac = acetylacetonate) with CH(PPh2)3 led to dinuclear complexes, [Ph2PCH(PPhAuPPh2)2CHPPh2][ClO4]2 or [PH2PC(PPh2AuPPh2)2CPPh2], with react further with [AuX(tht)] (X = C6F5 or Cl) or [Au(PPh3)(tht)]ClO4 to give tetranuclear cationic, [XAuPPh2CH(PPh2AuPPh2)2CHPPh2AuX][ClO4]2 or [(Ph3P)AuPPh2C(PPh2AuPPh2)2CPPh2Au(PPh3)] [ClO4]2, or neutral complexes, [XAuPPh2C(PPh2AuPPh2)2CPPh2AuX]. Trinuclear complexes, such as [CH(PPh2AuPPh2)3CH][ClO4]3 or [CH{PPh2Au(C6F5)}3], were obtained by reaction of [Au(tht)2]ClO4 or [Au(C6F5)(tht)] with CH(PPh2)3. Oxidation of [Ph2PC(PPhAuPPh2)2CPPh2] with H2O2 gives [(O)Ph2PC(PPhAuPPh2)2CPPh2(O)]. The structures of two forms of the latter compound have been established by X-ray crystallography. Both involve an eight-membered ring with a very short transannular gold-gold contact.