Abstract
We report herein the synthesis and characterization of a terminal Co(III) imido complex supported by an intermediate field N,N,C heteroscorpionate. This chemistry is enabled through the development of an additional member of this ligand type featuring Ph(2)(CH(3))C- substituents, one of which weakly binds and stabilizes Co in the corresponding Co(I) precursor. The Co(III) imide is low-spin with no evidence for thermal population of open-shell excited states. Unusually, the imido ligand in this molecule tilts markedly toward the C(alkyl) donor. DFT calculations suggest this structural feature to be largely a result of strong Co-C covalency, underscoring the importance of M-C bonding in determining the (electronic) structure of metal centers supported by this class of ligand.