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

Pankaj Kumar, Yong Min Lee, Young Jun Park, Maxime A. Siegler, Kenneth D. Karlin, Wonwoo Nam

Research output: Contribution to journalArticlepeer-review

27 Scopus citations

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(CH3CN)]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 KO2/2.2.2-cryptand to produce [(12-TMC)CoII(NO2)]+ (3) and [(13-TMC)CoII(NO2)]+ (4), respectively; these possess O,O′-chelated nitrito ligands. Mechanistic studies using 18O-labeled superoxide (18O2•-) showed that one O atom in the nitrito ligand is derived from superoxide and the O2 produced comes from the other superoxide O atom. Evidence supporting the formation of a Co-peroxynitrite intermediate is also presented.

Original languageEnglish
Pages (from-to)4284-4287
Number of pages4
JournalJournal of the American Chemical Society
Volume137
Issue number13
DOIs
StatePublished - 8 Apr 2015

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