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High‐Spin Imido Cobalt Complexes with Imidyl Radical Character **
Author(s) -
Reckziegel Alexander,
Kour Manjinder,
Battistella Beatrice,
Mebs Stefan,
Beuthert Katrin,
Berger Robert,
Werncke C. Gunnar
Publication year - 2021
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202103841
Subject(s) - cobalt , electron paramagnetic resonance , chemistry , nucleophile , substituent , crystallography , trigonal crystal system , absorption spectroscopy , trigonal prismatic molecular geometry , ligand (biochemistry) , medicinal chemistry , stereochemistry , crystal structure , inorganic chemistry , nuclear magnetic resonance , organic chemistry , physics , catalysis , octahedron , quantum mechanics , biochemistry , receptor
We report on the synthesis of a variety of trigonal imido cobalt complexes [Co(NAryl)L 2 ] − , (L=N(Dipp)SiMe 3 ), Dipp=2,6‐diisopropylphenyl) with very long Co−N Aryl bonds of around 1.75 Å. Their electronic structure was interrogated using a variety of physical and spectroscopic methods such as EPR or X‐Ray absorption spectroscopy which leads to their description as highly unusual imidyl cobalt complexes. Computational analyses corroborate these findings and further reveal that the high‐spin state is responsible for the imidyl character. Exchange of the Dipp substituent on the imide by the smaller mesityl function (2,4,6‐trimethylphenyl) effectuates the unexpected Me 3 Si shift from the ancillary ligand set to the imidyl nitrogen, revealing a highly reactive, nucleophilic character of the imidyl unit.