Gold(III) Phenylphosphides and -phosphodiides

In this paper we describe the synthesis of a series of cyclic and acyclic gold phosphine,
phosphide, and phosphodiide derivatives of the primary phosphine PPhH2. Thus, by reacting
[Au(C6F5)x(tht)] (x = 1, 3) with an equimolecular amount of PPhH2, the phosphino complexes
[Au(C6F5)x(PPhH2)] (x = 1, 3) are obtained. The gold(III) complex [Au(C6F5)3(PPhH2)] reacts
with gold(I), silver(I), or gold(III) reagents in the presence of a deprotonating agent, leading
to the new di- or trinuclear phenylphosphide derivatives [Au(C6F5)3(μ-PPhH)Au(PR3)] (R =
Ph, Me), PPN[{Au(C6F5)3}2(μ-PPhH)], or PPN[{Au(C6F5)3(μ-PPhH)}2M] (M = Au, Ag). The
anionic gold(III) complex PPN[{Au(C6F5)3}2(μ-PPhH)] further reacts with similar gold(I)
precursors to afford higher nuclearity phosphodiide species, such as PPN[{Au(C6F5)3}2(μ3-PPh){Au(PPh3)}], (PPN)2[{Au(C6F5)3}2(μ3-PPh){Au(C6F5)}], or (PPN)3[{(Au(C6F5)3)2(μ3-PPh)}2Au]. Furthermore, treatment of [Au(C6F5)2(μ-Cl)]2 with PPhH2 results in the formation of
the cyclic trinuclear complex [Au(C6F5)2(μ-PPhH)]3, which can further react with [Au(acac)(PPh3)] to afford the tetranuclear phosphide/phosphodiide derivative [{Au(C6F5)2(μ-PPhH)}2{Au(C6F5)2(μ3-PPh)Au(PPh3)}]. The crystal structures of compounds PPN[{Au(C6F5)3}2(μ-PPhH)], [{Au(C6F5)3}(μ3-PPh){Au(PPh3)}2], and [Au(C6F5)2(μ-PPhH)]3 have been determined
by X-ray diffraction methods.