Synthesis, Electronic Structure, and Reactivity of a Planar Four‐Coordinate, Cobalt–Imido Complex.

A four‐coordinate cobalt–imido complex, (tBumPNP)Co=NMes (tBumPNP=modified PNP pincer ligand) has been synthesized from addition of 2,4,6‐trimethylphenylazide (Mes–N3) to the corresponding dinitrogen complex. The solid‐state structure determined by X‐ray diffraction established a rare, idealized planar geometry with a Co=N bond distance of 1.716(2) Å. Magnetic measurements revealed an S=1 ground state with CAS‐SCF calculations supporting radical character on the imide nitrogen. Thermolysis of the cobalt–imido compound induced selective insertion of the imido group into a Co−P bond and yielded a three‐coordinate cobalt complex with a distorted T‐shaped geometry. Transition state analysis conducted with DFT calculations established the thermodynamic stability of the P–N coupled product and provided insight into the exclusive selectivity. [ABSTRACT FROM AUTHOR]