Synthesis, Structure and Reactivity of [(acac)AuCH(PPh2AuPPh2)2CHAu(acac)], a Complex Containing the Tridentate Ligand [HC(PPh2)2]−

The complex [(acac)AuCH(PPh2AuPPh2)2CHAu(acac)] (1) is obtained by various procedures: a) by reaction of [Ph3PAuCH (PPh2AuPPh2)2CHAuPPh3](ClO4) 2 with NBu4[Au(acac)Cl], b) by reaction of [ClAuCH(PPh2AuPPh2)2CHAuCl] with [Au(acac)PPh3] or with Tl(acac) and c) by reaction of [ClAuPPh2CH2PPh2AuCl] with Tl(acac). The acetylacetonato ligand can act as deprotonating agent; thus, complex 1 reacts with (phosphane)gold complexes, [Au(C6F5)2{(PPh2)2-CH2)]ClO4, [Au(C6F5)3(PPh2CH2PPh2)] or [Au(PPh3)2]ClO4, to give the hexanuclear complexes [(C6F5)2Au{(PPh2)2CH} AuCH(PPh2AuPPh2)2CHAu{CH(PPh2)2) Au(C6F5)2](ClO4)2, [(C6F5)3Au(PPh2CHPPh2)AuCH (PPh2AuPPh2)2CHAu-(PPh2CHPPh2)Au(C6F5)3] or [(Ph3PAu)2C(PPh2AuPPh2)2C-(AuPPh3)2](ClO4)2, respectively. The crystal structure of 1 has been established by X-ray crystallography and displays two independent eight-membered rings with inversion symmetry and short transannular gold-gold contacts. The first ab initio results for a transannular AuI-AuI interaction are reported.

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