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Redox non‐innocent ligands have recently emerged as interesting tools to obtain new reactivity with a wide variety of metals. However, gold has almost been neglected in this respect. Here, we report mechanistic investigations related to a rare example of ligand‐based redox chemistry in the coordination sphere of gold. The dinuclear metal‐centered mixed‐valent Au I –Au III  complex  1 , supported by monoanionic diarylamido‐diphosphine ligand PNP Pr  and with three chlorido ligands overall, undergoes a complex series of reactions upon halide abstraction by silver salt or Lewis acids such as gallium trichloride. Formation of the ultimate Au I –Au I  complex  2  requires the intermediacy of Au I –Au I  dimers  5  and  7  as well as the unique Au III –Au III  complex  6 , both of which are interconverted in a feedback loop. Finally, unprecedented  ortho ‐selective C−H activation of the redox‐active PNP ligand results in the carbazolyldiphosphine derivative PN*P Pr  via ligand‐to‐metal two‐electron transfer. This work demonstrates that the redox‐chemistry of gold may be significantly expanded and modified when using a reactive ligand scaffold.

Controlled Interconversion of a Dinuclear Au Species Supported by a Redox‐Active Bridging PNP Ligand Facilitates Ligand‐to‐Gold Electron Transfer