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Chromium(IV)-peroxo complex formation and its nitric oxide dioxygenase reactivity

Title
Chromium(IV)-peroxo complex formation and its nitric oxide dioxygenase reactivity
Authors
Yokoyama A.Han J.E.Cho J.Kubo M.Ogura T.Siegler M.A.Karlin K.D.Nam W.
Ewha Authors
남원우조재흥Kenneth D. Karlin
SCOPUS Author ID
남원우scopus
Issue Date
2012
Journal Title
Journal of the American Chemical Society
ISSN
0002-7863JCR Link
Citation
vol. 134, no. 37, pp. 15269 - 15272
Indexed
SCI; SCIE; SCOPUS WOS scopus
Abstract
The O2 and NO reactivity of a Cr(II) complex bearing a 12-membered tetraazamacrocyclic N-tetramethylated cyclam (TMC) ligand, [Cr II(12-TMC)(Cl)]+ (1), and the NO reactivity of its peroxo derivative, [CrIV(12-TMC)(O2)(Cl)]+ (2), are described. By contrast to the previously reported Cr(III)-superoxo complex, [CrIII(14-TMC)(O2)(Cl)]+, the Cr(IV)-peroxo complex 2 is formed in the reaction of 1 and O2. Full spectroscopic and X-ray analysis revealed that 2 possesses side-on ν2-peroxo ligation. The quantitative reaction of 2 with NO affords a reduction in Cr oxidation state, producing a Cr(III)-nitrato complex, [CrIII(12-TMC) (NO3)(Cl)]+ (3). The latter is suggested to form via a Cr(III)-peroxynitrite intermediate. [CrII(12-TMC)(NO)(Cl)] + (4), a Cr(II)-nitrosyl complex derived from 1 and NO, could also be synthesized; however, it does not react with O2. © 2012 American Chemical Society.
DOI
10.1021/ja307384e
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자연과학대학 > 화학·나노과학전공 > Journal papers
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