Generation, Spectroscopic Characterization, and Computational Analysis of a Six-Coordinate Cobalt(III)-Imidyl Complex with an Unusual = 3/2 Ground State that Promotes N-Group and Hydrogen Atom-Transfer Reactions with Exogenous Substrates.

We report the synthesis and characterization of a mononuclear nonheme cobalt(III)-imidyl complex, [Co(NTs)(TQA)(OTf)] (), with an = 3/2 spin state that is capable of facilitating exogenous substrate modifications. Complex was generated from the reaction of Co(TQA)(OTf) with PhINTs at -20 °C. A flow setup with ESI-MS detection was used to explore the kinetics of the formation, stability, and degradation pathway of in solution by treating the Co(II) precursor with PhINTs. Co K-edge XAS data revealed a distinct shift in the Co K-edge compared to the Co(II) precursor, in agreement with the formation of a Co(III) intermediate. The unusual = 3/2 spin state was proposed based on EPR, DFT, and CASSCF calculations and Co Kβ XES results. Co K-edge XAS and IR photodissociation (IRPD) spectroscopies demonstrate that is a six-coordinate species, and IRPD and resonance Raman spectroscopies are consistent with being exclusively the isomer with the NT ligand occupying the vacant site trans to the TQA aliphatic amine nitrogen atom. Electronic structure calculations (broken symmetry DFT and CASSCF/NEVPT2) demonstrate an = 3/2 oxidation state resulting from the strong antiferromagnetic coupling of an NTs spin to the high-spin = 2 Co(III) center. Reactivity studies of with PPh derivatives revealed its electrophilic characteristic in the nitrene-transfer reaction. While the activation of C-H bonds by was proved to be kinetically challenging, could oxidize weak O-H and N-H bonds. Complex is, therefore, a rare example of a Co(III)-imidyl complex capable of exogenous substrate transformations.