Ligand Redox Non-Innocence in [Coᴵᴵᴵ(TAML)]0/‒ Complexes Affects Nitrene Formation

The redox non-innocence of the TAML scaffold in cobalt-TAML (Tetra-Amido Macrocyclic Ligand) complexes has been under debate since 2006. In this work we demonstrate with a variety of spectroscopic measurements that the TAML backbone in the anionic complex [CoIII(TAMLred)]- is truly redox non-innocent, and that one-electron oxidation affords [CoIII(TAMLsq)]. Multi-reference (CASSCF) calculations show that the electronic structure of [CoIII(TAMLsq)] is best described as an intermediate spin (S = 1) cobalt(III) center that is antiferromagnetically coupled to a ligand-centered radical, affording an overall doublet (S = ½) ground-state. Reaction of the cobalt(III)-TAML complexes with PhINNs as a nitrene precursor leads to TAML-centered oxidation, and produces nitrene radical complexes without oxidation of the metal ion. The ligand redox state (TAMLred or TAMLsq) determines whether mono- or bis-nitrene radical complexes are formed. Reaction of [CoIII(TAMLsq)] or [CoIII(TAMLred)]- with PhINNs results in formation of [CoIII(TAMLq)(NNs)] and [CoIII(TAMLq)(NNs)2]-, respectively. Herein, ligand-to-substrate single-electron transfer results in one-electron reduced Fischer-type nitrene radicals (NNs-) that are intermediates in catalytic nitrene transfer to styrene. These nitrene radical species were characterized by EPR, XANES, and UV-Vis spectroscopy, high resolution mass spectrometry, magnetic moment measurements and supporting CASSCF calculations.