Imido Cobalt Complexes with Imidyl Character

01 March 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

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.

Keywords

Imido Complexes
cobalt ions
spectroscopic analysis
Bonding Analysis

Supplementary materials

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Description
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Title
Co Imidyl SI final
Description
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