Structure and Reactivity of a Manganese(VI) Nitrido Complex Bearing a Tetraamido Macrocyclic Ligand

Manganese complexes in +6 oxidation state are rare. Although a number of Mn­(VI) nitrido complexes have been generated in solution via one-electron oxidation of the corresponding Mn­(V) nitrido species, they are too unstable to isolate. Herein we report the isolation and the X-ray structure of a Mn­(VI) nitrido complex, [Mn^VI(N)­(TAML)]^– (2), which was obtained by one-electron oxidation of [Mn^V(N)­(TAML)]^2– (1). 2 undergoes N atom transfer to PPh₃ and styrenes to give Ph₃PNH and aziridines, respectively. A Hammett study for various p-substituted styrenes gives a V-shaped plot; this is rationalized by the ability of 2 to function as either an electrophile or a nucleophile. 2 also undergoes hydride transfer reactions with NADH analogues, such as 10-methyl-9,10-dihydroacridine (AcrH₂) and 1-benzyl-1,4-dihydronicotinamide (BNAH). A kinetic isotope effect of 7.3 was obtained when kinetic studies were carried out with AcrH₂ and AcrD₂. The reaction of 2 with NADH analogues results in the formation of [Mn^V(N)­(TAML-H⁺)]^– (3), which was characterized by ESI/MS, IR spectroscopy, and X-ray crystallography. These results indicate that this reaction occurs via an initial “separated CPET” (separated concerted proton–electron transfer) mechanism; that is, there is a concerted transfer of 1 e^– + 1 H⁺ from AcrH₂ (or BNAH) to 2, in which the electron is transferred to the Mn^VI center, while the proton is transferred to a carbonyl oxygen of TAML rather than to the nitrido ligand.