Reactions of Co(III) - Nitrosyl Complexes with Superoxide and Their Mechanistic Insights

Abstract

New CoIII-nitrosyl complexes bearing N-tetramethylated cyclam (TMC) ligands, [(12-TMC)CoIII(NO)]2+ (1) and [(13-TMC)CoIII(NO)]2+ (2), were synthesized via [(TMC)CoII(CH<inf>3</inf>CN)]2+ + NO(g) reactions. Spectroscopic and structural characterization showed that these compounds bind the nitrosyl moiety in a bent end-on fashion. Complexes 1 and 2 reacted with KO<inf>2</inf>/2.2.2-cryptand to produce [(12-TMC)CoII(NO<inf>2</inf>)]+ (3) and [(13-TMC)CoII(NO<inf>2</inf>)]+ (4), respectively; these possess O,O′-chelated nitrito ligands. Mechanistic studies using 18O-labeled superoxide (18O<inf>2</inf>•-) showed that one O atom in the nitrito ligand is derived from superoxide and the O<inf>2</inf> produced comes from the other superoxide O atom. Evidence supporting the formation of a Co-peroxynitrite intermediate is also presented. © 2015 American Chemical Society.