Two-fold proton coupled electron transfer of a Ta(<sc>v</sc>) aniline complex mediated by a redox active NNN pincer ligand

We report the proton-coupled electron transfer (PCET) reactivity of an octahedral Ta(v) aniline complex supported by an acridane-derived redox active NNN pincer ligand. The reversible binding of aniline to a Ta(v) dichloride induces significant coordination-induced bond weakening (CIBW) of the aniline N-H bonds. This enables a rare two-fold hydrogen atom abstraction, resulting in a terminal imido complex and a two-electron oxidation of the NNN pincer ligand, all while maintaining the metal's oxidation state. The bond dissociation free energies (BDFEs) of the aniline and a transient radical amido complex are estimated through stoichiometric reactions with different hydrogen atom abstractors and donors, further supported by density functional theory calculations.