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

The reaction of the cobalt(I) complex [(TIMMN(mes))Co(I)](BPh(4)) (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)](BPh(4)) (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(z(2))‐orbital of the cobalt ion and negative hyperconjugation with the neighboring methylene groups. One‐electron oxidation of 3 with [FeCp(2)](OTf) provides access to the rare, high‐valent cobalt(IV) imido complex [(TIMMN(mes))Co(IV)(NAd)](OTf)(2) (4). Despite a half‐life of less than 1 h at room temperature, 4 could be isolated at low temperatures in analytically pure form. Single‐crystal X‐ray diffractometry and EPR spectroscopy corroborate the molecular structure and the d(5) low‐spin, S= [Formula: see text] , electron configuration. A computational analysis of 4 suggests high covalency within the Co(IV)=NAd bond with non‐negligible spin density located at the imido moiety, which translates into substantial triplet nitrene character.