Inorganic Chemistry

Imido Cobalt Complexes with Imidyl Character


We report on the synthesis of a variety of trigonal imido cobalt complexes [Co(NAryl)L2), (L = N(Dipp)SiMe3), Dipp = 2,6-diisopropylphenyl) bearing very long Co–NAryl bonds of around 1.75 Å. The electronic structure was interrogated using a variety of physical and spectroscopic methods indicating the first authenticated examples of cobalt bound imidyl species. Computational studies corroborate these findings and reveal that the high-spin state of these complexes gives rise to unpaired spin-density on the imide nitrogen and leads to its imidyl character. Obtained complexes are capable of intermolecular H atom abstraction from C–H bonds that yields the corresponding cobalt amides. Exchange of the Dipp-substituent on the imide by the smaller mesityl function (2,4,6-trimethylphenyl) effectuates the unexpected Me3Si shift from the ancillary ligand set to the imide nitrogen, followed by intramolecular C–H bond activation.

Version notes

Version on first submission


Thumbnail image of Manuscript_imidyl_rxiv.pdf

Supplementary material

Thumbnail image of Co_Imidyl_SI_final.pdf
Co Imidyl SI final