Structure and Reactivity of One- and Two-Electron Oxidized Manganese(V) Nitrido Complexes Bearing a Bulky Corrole Ligand.

As a strategy to design stable but highly reactive metal nitrido species, we have synthesized a manganese(V) nitrido complex bearing a bulky corrole ligand, [Mn(N)(TTPPC)] (, TTPPC is the trianion of 5,10,15-Tris(2,4,6-triphenylphenyl)corrole). Complex is readily oxidized by 1 equiv of CpFe to give the neutral complex , which can be further oxidized by 1 equiv of [(-Br-CH)N][B(CF)] to afford the cationic complex . All three complexes are stable in the solid state and in CHCl solution, and their molecular structures have been determined by X-ray crystallography. Spectroscopic and theoretical studies indicate that complexes and are best formulated as Mn(V) nitrido π-cation corrole [Mn(N)(TTPPC)] and Mn(V) nitrido π-dication corrole [Mn(N)(TTPPC)], respectively. Complex is the most reactive N atom transfer reagent among isolated nitrido complexes; it reacts with PPh and styrene with second-order rate constants of 2.12 × 10 and 1.95 × 10 M s, respectively, which are >10 faster than that of .