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

ABSTRACT: The O(2) 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, [Cr(IV)(12-TMC)(O(2))(Cl)](+) (2), are described. By contrast to the previously reported Cr(III)-superoxo complex, [Cr(III)(14-TMC)(O(2))(Cl)](+), the Cr(IV)-peroxo complex 2 is formed in the reaction of 1 and O(2). Full spectroscopic and X-ray analysis revealed that 2 possesses side-on ?(2)-peroxo ligation. The quantitative reaction of 2 with NO affords a reduction in Cr oxidation state, producing a Cr(III)-nitrato complex, [Cr(III)(12-TMC)(NO(3))(Cl)](+) (3). The latter is suggested to form via a Cr(III)-peroxynitrite intermediate. [Cr(II)(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 O(2).

SUBMITTER: Yokoyama A

PROVIDER: S-EPMC3496875 | biostudies-literature | 2012 Sep

REPOSITORIES: biostudies-literature

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

Yokoyama Atsutoshi A Han Jung Eun JE Cho Jaeheung J Kubo Minoru M Ogura Takashi T Siegler Maxime A MA Karlin Kenneth D KD Nam Wonwoo W

Journal of the American Chemical Society 20120910 37

The O(2) 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, [Cr(IV)(12-TMC)(O(2))(Cl)](+) (2), are described. By contrast to the previously reported Cr(III)-superoxo complex, [Cr(III)(14-TMC)(O(2))(Cl)](+), the Cr(IV)-peroxo complex 2 is formed in the reaction of 1 and O(2). Full spectroscopic and X-ray analysis revealed that 2 possesses side-on η(2)-pe ...[more]

PMID: 22950528

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