Four-Coordinate Co(III) Imide with an Unusually Tilted Terminal Imido Ligand

Li Gu; Addison Fraker; Niklas B Thompson; Alex McSkimming

doi:10.1021/acs.organomet.3c00473

Four-Coordinate Co(III) Imide with an Unusually Tilted Terminal Imido Ligand

Organometallics. 2024 Jan 12;43(3):341-348. doi: 10.1021/acs.organomet.3c00473. eCollection 2024 Feb 12.

Authors

Li Gu¹, Addison Fraker¹, Niklas B Thompson², Alex McSkimming¹

Affiliations

¹ Department of Chemistry, Tulane University, New Orleans, Louisiana 70118, United States.
² Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States.

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 Ph₂(CH₃)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.