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

Atsutoshi Yokoyama; Jung Eun Han; Jaeheung Cho; Minoru Kubo; Takashi Ogura; Maxime A. Siegler; Kenneth D. Karlin; Wonwoo Nam

doi:10.1021/ja307384e

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

Atsutoshi Yokoyama, Jung Eun Han, Jaeheung Cho, Minoru Kubo, Takashi Ogura, Maxime A. Siegler, Kenneth D. Karlin, Wonwoo Nam

Department of Chemistry & Nanoscience

Research output: Contribution to journal › Article › peer-review

68 Scopus citations

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, [Cr^IV(12-TMC)(O₂)(Cl)]⁺ (2), are described. By contrast to the previously reported Cr(III)-superoxo complex, [Cr^III(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, [Cr^III(12-TMC) (NO₃)(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 O₂.

Original language	English
Pages (from-to)	15269-15272
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	134
Issue number	37
DOIs	https://doi.org/10.1021/ja307384e
State	Published - 19 Sep 2012

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@article{77057465ba7e418784f824f8586f0d97,

title = "Chromium(IV)-peroxo complex formation and its nitric oxide dioxygenase reactivity",

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.",

author = "Atsutoshi Yokoyama and Han, {Jung Eun} and Jaeheung Cho and Minoru Kubo and Takashi Ogura and Siegler, {Maxime A.} and Karlin, {Kenneth D.} and Wonwoo Nam",

year = "2012",

month = sep,

day = "19",

doi = "10.1021/ja307384e",

language = "English",

volume = "134",

pages = "15269--15272",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "37",

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TY - JOUR

T1 - Chromium(IV)-peroxo complex formation and its nitric oxide dioxygenase reactivity

AU - Yokoyama, Atsutoshi

AU - Han, Jung Eun

AU - Cho, Jaeheung

AU - Kubo, Minoru

AU - Ogura, Takashi

AU - Siegler, Maxime A.

AU - Karlin, Kenneth D.

AU - Nam, Wonwoo

PY - 2012/9/19

Y1 - 2012/9/19

N2 - 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.

AB - 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.

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U2 - 10.1021/ja307384e

DO - 10.1021/ja307384e

M3 - Article

C2 - 22950528

AN - SCOPUS:84866519999

SN - 0002-7863

VL - 134

SP - 15269

EP - 15272

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 37

ER -

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

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