A Family of Alkynylgold(III) Complexes [Au<sup>I</sup>(μ-{CH<sub>2</sub>}<sub>2</sub>PPh<sub>2</sub>)<sub>2</sub>Au<sup>III</sup>(C⋮CR)<sub>2</sub>] (R = Ph, <i><sup>t</sup></i><sup></sup>Bu, Me<sub>3</sub>Si): Facile and Reversible Comproportionation of Gold(I)/Gold(III) to Digold(II)
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The symmetric digold(II)dichloride bis(ylide) complex [Au2Cl2(μ-{CH2}2PPh2)2] reacts with acetylides to form the asymmetric heterovalent gold(I)/gold(III) complexes [AuI(μ-{CH2}2PPh2)2AuIII(C⋮CR)2] [R = Ph, tBu, and SiMe3], the phenyl analogue of which was characterized by X-ray crystallography. These compounds represent the first examples of gold(III) complexes containing two acetylide ligands. [AuI(μ-{CH2}2PPh2)2AuIII(C⋮CPh)2] undergoes a reversible comproportionation reaction upon treatment with [Ag(ClO4)tht] to give the symmetric digold(II) cationic complex [Au2(tht)2(μ-{CH2}2PPh2)2](ClO4)2. If this complex is treated with phenylacetylene in the presence of base, the heterovalent gold(I)/gold(III) complex is re-formed. This reversible interconversion between binuclear gold(I)/gold(III) and digold(II) bis(ylide) complexes is unprecedented.
