Structure and Reactivity of One- and Two-Electron OxidizedManganese(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) nitridocomplex bearing a bulky corrole ligand, [MnV(N)(TTPPC)]-(1, TTPPC is the trianion of 5,10,15-Tris(2,4,6-triphenylphenyl)-corrole). Complex1is readily oxidized by 1 equiv of Cp2Fe+to give the neutral complex2, which can be further oxidized by 1 equivof [(p-Br-C6H4)3N center dot+][B(C6F5)4]toafford the cationic complex3. All three complexes are stable in the solid state and in CH2Cl2solution, and their molecular structures have been determined by X-ray crystallography. Spectroscopic and theoretical studiesindicate that complexes2and3are best formulated as Mn(V) nitrido pi-cation corrole [MnV(N)(TTPPC+center dot)] and Mn(V) nitrido pi-dication corrole [MnV(N)(TTPPC2+)]+, respectively. Complex3is the most reactive N atom transfer reagent among isolated nitridocomplexes; it reacts with PPh3and styrene with second-order rate constants of 2.12x105and 1.95x10-2M-1s-1, respectively, which are >107faster than that of 2