A Pair of Cobalt(III/IV) Terminal Imido Complexes.

ABSTRACT: The reaction of the cobalt(I) complex [(TIMMN^mes )Co^I ](BPh₄ ) (2) (TIMMN^mes =tris-[2-(3-mesitylimidazolin-2-ylidene)methyl]amine) with 1-adamantylazide yields the cobalt(III) imido complex [(TIMMN^mes )Co^III (NAd)](BPh₄ ) (3) with concomitant release of dinitrogen. The N-anchor in diamagnetic 3 features an unusual, planar tertiary amine, which results from repulsive electrostatic interaction with the filled d(z² )-orbital of the cobalt ion and negative hyperconjugation with the neighboring methylene groups. One-electron oxidation of 3 with [FeCp₂ ](OTf) provides access to the rare, high-valent cobalt(IV) imido complex [(TIMMN^mes )Co^IV (NAd)](OTf)₂ (4). Despite

SUBMITTER: Mao W 

PROVIDER: S-EPMC8362208 | biostudies-literature | 2021 Jul

REPOSITORIES: biostudies-literature