Photoinitiated Oxidative Addition of CF3I to Gold(I) and Facile Aryl-CF3 Reductive Elimination

Herein we report the mechanism of oxidative addition of CF3I to Au­(I), and remarkably fast Caryl–CF3 bond reductive elimination from Au­(III) cations. CF3I undergoes a fast, formal oxidative addition to R3PAuR′ (R = Cy, R′ = 3,5-F2-C6H4, 4-F-C6H4, C6H5, 4-Me-C6H4, 4-MeO-C6H4, Me; R = Ph, R′ = 4-F-C6H4, 4-Me-C6H4). When R′ = aryl, complexes of the type R3PAu­(aryl)­(CF3)I can be isolated and characterized. Mechanistic studies suggest that near-ultraviolet light (λmax = 313 nm) photoinitiates a radical chain reaction by exciting CF3I. Complexes supported by PPh3 undergo reversible phosphine dissociation at 110 °C to generate a three-coordinate intermediate that undergoes slow reductive elimination. These processes are quantitative and heavily favor Caryl–I reductive elimination over Caryl–CF3 reductive elimination. Silver-mediated halide abstraction from all complexes of the type R3PAu­(aryl)­(CF3)I results in quantitative formation of Ar–CF3 in less than 1 min at temperatures as low as −10 °C.