Methyl-, Ethenyl-, and Ethynyl-Bridged Cationic Digold Complexes Stabilized by Coordination to a Bulky Terphenylphosphine Ligand.

Reactions of the gold(I) triflimide complex [Au(NTf2 )(PMe2 Ar${{^{{\rm Dipp}{_{2}}}}}$)] (1) with the gold(I) hydrocarbyl species [AuR(PMe2 Ar${{^{{\rm Dipp}{_{2}}}}}$)] (2 a-2 c) enable the isolation of hydrocarbyl-bridged cationic digold complexes with the general composition [Au2 (μ-R)(PMe2 Ar${{^{{\rm Dipp}{_{2}}}}}$)2 ][NTf2 ], where Ar${{^{{\rm Dipp}{_{2}}}}}$=C6 H3 -2,6-(C6 H3 -2,6-iPr2 )2 and R=Me (3), CHCH2 (4), or CCH (5). Compound 3 is the first alkyl-bridged digold complex to be reported and features a symmetric [Au(μ-CH3 )Au](+) core. Complexes 4 and 5 are the first species of their kind that contain simple, unsubstituted vinyl and acetylide units, respectively. In the series of complexes 3-5, the bridging carbon atom systematically changes its hybridization from sp(3) to sp(2) and sp. Concomitant with this change, and owing to variations in the nature of the bonding within the [Au(μ-R)Au](+) unit, there is a gradual decrease in aurophilicity, that is, the strength of the Au⋅⋅⋅Au bonding interaction decreases. This change is illustrated by a monotonic increase in the Au-Au distance by approximately 0.3 Å from R=CH3 (2.71 Å) to CHCH2 (3.07 Å) and CCH (3.31 Å).