Redox Noninnocence of a β‐Diketiminate Enabling Electron Transfer Catalysis

The β‐diketiminate is an iconic class of ligand that spans a wide variety of metal complexes across the periodic table. Compared to the well‐evaluated redox noninnocent nature of several other ligand classes, detectable redox activity for β‐diketiminate is scarce. The development of an effective homogeneous catalyst leveraging the redox reservoir property of a β‐diketiminate backbone has never been achieved. Herein, we present a copper bis(β‐diketiminate) complex that enables the completely ligand‐centric redox for steering alkoxycarboxylation at the 2‐position of indole. The success of the reaction pivots on the electron reservoir property of an electron‐rich β‐diketiminate that can facilitate single electron transfer to reductively cleave a C─Br bond. X‐ray structure determination of the complex, along with CV, EPR, and magnetic susceptibility, describes the electronic structure of the catalyst molecule and proves the ligand's predominant role in such single‐electron transfer catalysis.