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Imido Cobalt Complexes with Imidyl Character

preprint
submitted on 26.02.2021, 21:52 and posted on 01.03.2021, 12:32 by alexander Reckziegel, Manjinder Kour, Beatrice Battistella, Stefan Mebs, Katrin Beuthert, Robert Berger, Gunnar Werncke
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.

Funding

DFG WE 5627/4-1

History

Email Address of Submitting Author

gunnar.werncke@chemie.uni-marburg.de

Institution

Philipps-University Marburg

Country

Germany

ORCID For Submitting Author

0000-0002-9963-8391

Declaration of Conflict of Interest

No conflict of interest

Version Notes

Version on first submission

Exports