A peroxynitrite complex of copper: formation from a copper-nitrosyl complex, transformation to nitrite and exogenous phenol oxidative coupling or nitration.
Reaction of nitrogen monoxide with a copper(I) complex possessing a tridentate alkylamine ligand gives a Cu(I)-(*NO) adduct, which when exposed to dioxygen generates a peroxynitrite (O=NOO(-))-Cu(II) species. This undergoes thermal transformation to produce a copper(II) nitrito (NO(2) (-)) complex and 0.5 mol equiv O(2). In the presence of a substituted phenol, the peroxynitrite complex effects oxidative coupling, whereas addition of chloride ion to dissociate the peroxynitrite moiety instead leads to phenol ortho nitration. Discussions include the structures (including electronic description) of the copper-nitrosyl and copper-peroxynitrite complexes and the formation of the latter, based on density functional theory calculations and accompanying spectroscopic data.
Park
Ga Young
GY
Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, USA.
Deepalatha
Subramanian
S
Puiu
Simona C
SC
Lee
Dong-Heon
DH
Mondal
Biplab
B
Narducci Sarjeant
Amy A
AA
del Rio
Diego
D
Pau
Monita Y M
MY
Solomon
Edward I
EI
Karlin
Kenneth D
KD
D003300:Copper / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009566:Nitrates / Q000737:chemistry*; D009569:Nitric Oxide / Q000737:chemistry; D009573:Nitrites / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry; D030421:Peroxynitrous Acid / Q000737:chemistry*; D010636:Phenols / Q000737:chemistry*
D009566:Nitrates; D009573:Nitrites; D010636:Phenols; D030421:Peroxynitrous Acid; D009569:Nitric Oxide; D003300:Copper; D010100:Oxygen