Ability of a Au(III)-N unit to bond two aurophilically interacting gold(I)centers

The monohapto neutral 2-(diphenylphosphino)aniline (PNH2) complexes [Au(C6F 5)(2)X(PNH2)] (X = C6F5 (1), Cl (2)) have been obtained from [Au(C6F5)(3)(t ht)] or [Au(C6F5)(2)(mu -Cl)](2) and PNH2, and the cationic [Au(C6F5)(2)-(P NH2)]-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 = acetylace tonate) or by treatment of the chloro complex 2 with Tl(acac). It reacts wi th [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 obt ained by reaction of equimolar amounts of 3 and [Au(acac)(PPh3)1; 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 co mplexes 2-4 and 7 have been established by X-ray crystallography; the last- mentioned displays an unusual Au(I)-Au(III) interaction.