Synthesis of a cobalt(iv) ketimide with a squashed tetrahedral geometry

Oxidation of [Li(THF)]2[Co(N=C(t)Bu2)4] with 1 equiv. of I2 generates Co(N=C(t)Bu2)4 in 85% yield. In the solid-state, this complex exhibits a squashed tetrahedral structure about the Co center. DFT calculations reveal this geometry arises, in part, to maximize ketimide-to-cobalt π-donation.