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Organometallic gold complexes are used in a range of catalytic reactions, and they often serve as catalyst precursors that mediate C-C bond formation. In this study, we investigate C-C coupling to form ethane from various phosphine-ligated gem-digold(I) methyl complexes including [Au 2 (μ-CH 3 )(PMe 2 Ar') 2 ][NTf 2 ], [Au 2 (μ-CH 3 )(XPhos) 2 ][NTf 2 ], and [Au 2 (μ-CH 3 )(  t  BuXPhos) 2 ][NTf 2 ] {Ar' = C 6 H 3 -2,6-(C 6 H 3 -2,6-Me) 2 , C 6 H 3 -2,6-(C 6 H 2 -2,4,6-Me) 2 , C 6 H 3 -2,6-(C 6 H 3 -2,6-  i  Pr) 2 , or C 6 H 3 -2,6-(C 6 H 2 -2,4,6-  i  Pr) 2 ; XPhos = 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl;  t  BuXPhos = 2-di- tert -butylphosphino-2',4',6'-triisopropylbiphenyl; NTf 2 = bis(trifluoromethyl sulfonylimide)}. The gem-digold methyl complexes are synthesized through reaction between Au(CH 3 )L and Au(L)(NTf 2 ) {L = phosphines listed above}. For [Au 2 (μ-CH 3 )(XPhos) 2 ][NTf 2 ] and [Au 2 (μ-CH 3 )(  t  BuXPhos) 2 ][NTf 2 ], solid-state X-ray structures have been elucidated. The rate of ethane formation from [Au 2 (μ-CH 3 )(PMe 2 Ar') 2 ][NTf 2 ] increases as the steric bulk of the phosphine substituent Ar' decreases. Monitoring the rate of ethane elimination reactions by multinuclear NMR spectroscopy provides evidence for a second-order dependence on the gem-digold methyl complexes. Using experimental and computational evidence, it is proposed that the mechanism of C-C coupling likely involves (1) cleavage of [Au 2 (μ-CH 3 )(PMe 2 Ar') 2 ][NTf 2 ] to form Au(PR 2 Ar')(NTf 2 ) and Au(CH 3 )(PMe 2 Ar'), (2) phosphine migration from a second equivalent of [Au 2 (μ-CH 3 )(PMe 2 Ar') 2 ][NTf 2 ] aided by binding of the Lewis acidic [Au(PMe 2 Ar')] + , formed in step 1, to produce [Au 2 (CH 3 )(PMe 2 Ar')][NTf 2 ] and [Au 2 (PMe 2 Ar')] + , and (3) recombination of [Au 2 (CH 3 )(PMe 2 Ar')][NTf 2 ] and Au(CH 3 )(PMe 2 Ar') to eliminate ethane.

Reductive C–C Coupling from Molecular Au(I) Hydrocarbyl Complexes: A Mechanistic Study