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

72 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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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.

UR - https://www.scopus.com/pages/publications/84866519999

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

Abstract

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