Cobalt-Carbon Bonding in a Salen-Supported Cobalt(IV) Alkyl Complex Postulated in Oxidative MHAT Catalysis

The catalytic hydrofunctionalization of alkenes through radical-polar crossover metal hydrogen atom transfer (MHAT) offers a mild pathway for the introduction of functional groups in sterically congested environments. For M = Co, this reaction is often proposed to proceed through secondary alkylcobalt(IV) intermediates, which have not been characterized unambiguously. Here, we characterize a metastable (salen)Co(isopropyl) cation, which is capable of forming C-O bonds with alcohols as proposed in the catalytic reaction. Electron nuclear double resonance (ENDOR) spectroscopy of this formally cobalt(IV) species establishes the presence of the cobalt-carbon bond, and accompanying DFT calculations indicate that the unpaired electron is localized on the cobalt center. Both experimental and computational studies show that the cobalt(IV)-carbon bond is stronger than the analogous bond in its cobalt(III) analogue, which is opposite of the usual oxidation state trend of bond energies. This phenomenon is attributable to an inverted ligand field that gives the bond Co^δ--C^δ+ character and explains its electrophilic reactivity at the alkyl group. The inverted Co-C bond polarity also stabilizes the formally cobalt(IV) alkyl complex so that it is accessible at unusually low potentials. Even another cobalt(III) complex, [(salen)Co^III]⁺, is capable of oxidizing (salen)Co^III(iPr) to the formally cobalt(IV) state. These results give insight into the electronic structure, energetics, and reactivity of a key reactive intermediate in oxidative MHAT catalysis.