Reaction of a copper-dioxygen complex with nitrogen monoxide (•NO) leads to a copper(II)-peroxynitrite species

Debabrata Maiti; Dong Heon Lee; Amy A. Narducci Sarjeant; Monita Y.M. Pau; Edward I. Solomon; Katya Gaoutchenova; Jörg Sundermeyer; Kenneth D. Karlin

doi:10.1021/ja801540e

Reaction of a copper-dioxygen complex with nitrogen monoxide (•NO) leads to a copper(II)-peroxynitrite species

Debabrata Maiti
, Dong Heon Lee
, Amy A. Narducci Sarjeant
, Monita Y.M. Pau
, Edward I. Solomon
, Katya Gaoutchenova
, Jörg Sundermeyer
, Kenneth D. Karlin

Department of Chemistry

Johns Hopkins University
Stanford University
University of Marburg

Research output: Contribution to journal › Journal article › peer-review

78 Scopus citations

Abstract

A discrete peroxynitrite-copper(II) complex, [(TMG₃tren)Cu^II(^-OON=O)]⁺(3), has been generated in solution (ESI-MS, m/z = 565.15; tetragonal EPR) by reacting ·NO(_g) with superoxo complex [(TMG₃tren)Cu^II(O₂·^-)]⁺ (2). Complex 3 undergoes a thermal transformation to give Cu^II-nitrite complex [(TMG₃tren)Cu^II(-ONO)]⁺ (4) (X-ray) along with ca. 0.5 molar equiv dioxygen. A DFT calculation derived structure with cyclic bidentate k²-O,O′-OONO bound peroxynitrite moiety and d_x2-y2 ground state is proposed. Experiments using ¹⁸O₂ suggest that the adjacent peroxo oxygen atoms in 3 are derived from molecular oxygen. Further, ¹⁸O₂ containing 3 undergoes O-O bond cleavage to form singly 18-O-labeled 4. The results suggest the viability of biological Cu^I/O₂/(·NO) peroxynitrite formation and chemistry, that is, not coming from free superoxide plus ·NO reaction.

Original language	English
Pages (from-to)	6700-6701
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	130
Issue number	21
DOIs	https://doi.org/10.1021/ja801540e
State	Published - 2008.05.28

Quacquarelli Symonds(QS) Subject Topics

Engineering - Petroleum
Engineering - Chemical
Chemistry
Biological Sciences

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@article{0651dc4ddd7c4d3f8ea49830f85aa195,

title = "Reaction of a copper-dioxygen complex with nitrogen monoxide (•NO) leads to a copper(II)-peroxynitrite species",

abstract = "A discrete peroxynitrite-copper(II) complex, [(TMG3tren)CuII(-OON=O)]+(3), has been generated in solution (ESI-MS, m/z = 565.15; tetragonal EPR) by reacting ·NO(g) with superoxo complex [(TMG3tren)CuII(O2·-)]+ (2). Complex 3 undergoes a thermal transformation to give CuII-nitrite complex [(TMG3tren)CuII(-ONO)]+ (4) (X-ray) along with ca. 0.5 molar equiv dioxygen. A DFT calculation derived structure with cyclic bidentate k2-O,O′-OONO bound peroxynitrite moiety and dx2-y2 ground state is proposed. Experiments using 18O2 suggest that the adjacent peroxo oxygen atoms in 3 are derived from molecular oxygen. Further, 18O2 containing 3 undergoes O-O bond cleavage to form singly 18-O-labeled 4. The results suggest the viability of biological CuI/O2/(·NO) peroxynitrite formation and chemistry, that is, not coming from free superoxide plus ·NO reaction.",

author = "Debabrata Maiti and Lee, \{Dong Heon\} and \{Narducci Sarjeant\}, \{Amy A.\} and Pau, \{Monita Y.M.\} and Solomon, \{Edward I.\} and Katya Gaoutchenova and J{\"o}rg Sundermeyer and Karlin, \{Kenneth D.\}",

year = "2008",

month = may,

day = "28",

doi = "10.1021/ja801540e",

language = "English",

volume = "130",

pages = "6700--6701",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

number = "21",

}

TY - JOUR

T1 - Reaction of a copper-dioxygen complex with nitrogen monoxide (•NO) leads to a copper(II)-peroxynitrite species

AU - Maiti, Debabrata

AU - Lee, Dong Heon

AU - Narducci Sarjeant, Amy A.

AU - Pau, Monita Y.M.

AU - Solomon, Edward I.

AU - Gaoutchenova, Katya

AU - Sundermeyer, Jörg

AU - Karlin, Kenneth D.

PY - 2008/5/28

Y1 - 2008/5/28

N2 - A discrete peroxynitrite-copper(II) complex, [(TMG3tren)CuII(-OON=O)]+(3), has been generated in solution (ESI-MS, m/z = 565.15; tetragonal EPR) by reacting ·NO(g) with superoxo complex [(TMG3tren)CuII(O2·-)]+ (2). Complex 3 undergoes a thermal transformation to give CuII-nitrite complex [(TMG3tren)CuII(-ONO)]+ (4) (X-ray) along with ca. 0.5 molar equiv dioxygen. A DFT calculation derived structure with cyclic bidentate k2-O,O′-OONO bound peroxynitrite moiety and dx2-y2 ground state is proposed. Experiments using 18O2 suggest that the adjacent peroxo oxygen atoms in 3 are derived from molecular oxygen. Further, 18O2 containing 3 undergoes O-O bond cleavage to form singly 18-O-labeled 4. The results suggest the viability of biological CuI/O2/(·NO) peroxynitrite formation and chemistry, that is, not coming from free superoxide plus ·NO reaction.

AB - A discrete peroxynitrite-copper(II) complex, [(TMG3tren)CuII(-OON=O)]+(3), has been generated in solution (ESI-MS, m/z = 565.15; tetragonal EPR) by reacting ·NO(g) with superoxo complex [(TMG3tren)CuII(O2·-)]+ (2). Complex 3 undergoes a thermal transformation to give CuII-nitrite complex [(TMG3tren)CuII(-ONO)]+ (4) (X-ray) along with ca. 0.5 molar equiv dioxygen. A DFT calculation derived structure with cyclic bidentate k2-O,O′-OONO bound peroxynitrite moiety and dx2-y2 ground state is proposed. Experiments using 18O2 suggest that the adjacent peroxo oxygen atoms in 3 are derived from molecular oxygen. Further, 18O2 containing 3 undergoes O-O bond cleavage to form singly 18-O-labeled 4. The results suggest the viability of biological CuI/O2/(·NO) peroxynitrite formation and chemistry, that is, not coming from free superoxide plus ·NO reaction.

UR - https://www.scopus.com/pages/publications/44349173665

U2 - 10.1021/ja801540e

DO - 10.1021/ja801540e

M3 - Journal article

C2 - 18457392

AN - SCOPUS:44349173665

SN - 0002-7863

VL - 130

SP - 6700

EP - 6701

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 21

ER -

Reaction of a copper-dioxygen complex with nitrogen monoxide (•NO) leads to a copper(II)-peroxynitrite species

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