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

Title
Reactions of Co(III) - Nitrosyl Complexes with Superoxide and Their Mechanistic Insights
Authors
Kumar P.Lee Y.-M.Park Y.J.Siegler M.A.Karlin K.D.Nam W.
Ewha Authors
남원우이용민
SCOPUS Author ID
남원우scopus; 이용민scopusscopus
Issue Date
2015
Journal Title
Journal of the American Chemical Society
ISSN
0002-7863JCR Link
Citation
vol. 137, no. 13, pp. 4284 - 4287
Publisher
American Chemical Society
Indexed
SCI; SCIE; SCOPUS WOS scopus
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.
DOI
10.1021/ja513234b
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자연과학대학 > 화학·나노과학전공 > Journal papers
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