Carbon–Phosphorus Coupling from C^N Cyclometalated Au(III) Complexes

With the aim of exploiting new organometallic species for cross‐coupling reactions, we report here on the Au(III)‐mediated C(aryl)−P bond formation occurring upon reaction of C^N cyclometalated Au(III) complexes with phosphines. The [Au(C^N)Cl(2)] complex 1 featuring the bidentate 2‐benzoylpyridine (C(CO)N) scaffold was found to react with PTA (1,3,5‐triaza‐7‐phosphaadamantane) under mild conditions, including in water, to afford the corresponding phosphonium 5 through C−P reductive elimination. A mechanism is proposed for the title reaction based on in situ (31)P{(1)H} NMR and HR‐ESI‐MS analyses combined with DFT calculations. The C−P coupling has been generalized to other C^N cyclometalated Au(III) complexes and other tertiary phosphines. Overall, this work provides new insights into the reactivity of cyclometalated Au(III) compounds and establishes initial structure–activity relationships to develop Au(III)‐mediated C−P cross‐coupling reactions.