Unexplored Facet of Pincer Ligands: Super-Reductant Behavior Applied to Transition-Metal-Free Catalysis.

Pincer ligands are well-established supporting ancillaries to afford robust coordination to metals across the periodic table. Despite their widespread use in developing homogeneous catalysts, the redox noninnocence of the ligand backbone is less utilized in steering catalytic transformations. This report showcases a trianionic, symmetric NNN-pincer to drive C-C cross-coupling reactions and heterocycle formation via C-H functionalization, without any coordination to transition metals. The starting substrates are aryl chlorides that can tease the limit of a catalyst's ability to promote a reductive cleavage at a much demanding potential of -2.90 V vs SCE. The reducing power of the simple trianionic ligand backbone has been tremendously amplified by shining visible light on it. The catalyst's success relies on its easy access to the one-electron oxidized iminosemiquinonate form that has been thoroughly characterized by X-band electron paramagnetic resonance spectroscopy through spectroelectrochemical experiments. The moderately long-lived excited-state lifetime (10.2 ns) and such a super-reductive ability dependent on the one-electron redox shuttle between the bisamido and iminosemiquinonato forms make this catalysis effective.