期刊
INORGANIC CHEMISTRY
卷 52, 期 19, 页码 11608-11617出版社
AMER CHEMICAL SOC
DOI: 10.1021/ic401975f
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资金
- U.S. National Science Foundation [CHE-0848397]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1306644] Funding Source: National Science Foundation
Studies by others suggest that the reduced vitamin B-12 complex, cob(II)alamin, scavenges nitric oxide to form air-sensitive nitroxylcobalamin (NO--Cbl(III); NOCbl) in vivo. The fate of newly formed NOCbl is not known. A detailed mechanistic investigation of the oxidation of NOCbl by oxygen is presented. Only base-on NOCbl reacts with O-2, and the reaction proceeds via an associative mechanism involving a peroxynitritocob(III)alamin intermediate, CO(III)-N(O)OO-. The intermediate undergoes O-O bond homolysis and ligand isomerization to ultimately yield NO(2)Cbl and H(2)OCbl(-)/HOCbl, respectively. Ligand isomerization may potentially occur independent of O-O bond homolysis. Formation of (OH)-O-center dot and (NO2)-N-center dot intermediates from O-O bond homolysis is demonstrated using phenol and tyrosine radical traps and the characterization of small amounts of a corrinoid product with minor modifications to the corrin ring.
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