Formation of a Cobalt(III) Imido from a Cobalt(II) Amido Complex. Evidence for Proton-Coupled Electron Transfer

The cobalt(II) amido complex, LCoNHtBu (L = bulky tris(carbene)borate) reacts with the 2,4,6-tri(tert-butyl)phenoxy radical to form the cobalt(III) imido, LCoNtBu. A computational investigation (SDD and 6-31G*) of possible reaction pathways provides evidence for a mechanism involving concerted proton-coupled electron transfer. The N−H BDE is computationally estimated to be 75 kcal/mol.