Di-, tri- and tetra-nuclear gold(I) complexes with Tris(diphenylphosphino)-methane or -methanide as ligand. Crystal structures of two modifications of [(O)Ph2PC(PPh2AuPPh2)2CPPh2(O)]·4CH2Cl2

Abstract

The reaction of [Au(tht)₂]ClO₄ or [Au(acac)(PPh₃)](tht = tetrahydrothiophene, acac = acetylacetonate) with CH(PPh₂)₃ led to dinuclear complexes, [Ph₂PCH(PPh₂AuPPh₂)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)₂ CHPPh₂AuX][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(PPh₂AuPPh₂)₂CPPh₂] with H₂O₂ gives [(O)Ph₂PC(PPh₂AuPPh₂)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.