Ability of a Au(III)−N Unit to Bond Two Aurophilically Interacting Gold(I) Centers

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Abstract
The monohapto neutral 2-(diphenylphosphino)aniline (PNH2) complexes [Au(C6F5)2X(PNH2)] (X = C6F5 (1), Cl (2)) have been obtained from [Au(C6F5)3(tht)] or [Au(C6F5)2(μ-Cl)]2 and PNH2, and the cationic [Au(C6F5)2(PNH2)]ClO4 (3) has been similarly prepared from [Au(C6F5)2(OEt2)2]ClO4 and PNH2 or from 2 and AgClO4. The neutral amido complex [Au(C6F5)2(PNH)] (4) can be obtained by deprotonation of 3 with PPN(acac) (acac = acetylacetonate) or by treatment of the chloro complex 2 with Tl(acac). It reacts with [Ag(OClO3)(PPh3)] or [Au(OClO3)(PPh3)] to give the dinuclear species [Au(C6F5)2{PNH(MPPh3)}]ClO4 (M = Ag (5), Au (6)). The latter can also be obtained by reaction of equimolar amounts of 3 and [Au(acac)(PPh3)]; when the molar ratio of the same reagents is 1:2, the trinuclear cationic complex [Au(C6F5)2{PN(AuPPh3)2}]ClO4 (7) is obtained. The crystal structures of complexes 2−4 and 7 have been established by X-ray crystallography; the last-mentioned displays an unusual Au(I)−Au(III) interaction.