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Kinetics and mechanism of oxygen transfer in the reaction of p-cyano-N,N-dimethylaniline N-oxide atom transfer to and from (meso-tetrakis(pentafluorophenyl)porphinato)iron(III) chloride

Journal Article · · J. Am. Chem. Soc.; (United States)
DOI:https://doi.org/10.1021/ja00245a041· OSTI ID:6368183
The authors report herein an investigation of the reaction of NO with (meso-tetrakis(pentafluorophenyl)porphinato)iron(III) chloride ((F/sub 20/TPP)Fe/sup III/Cl). The salt (F/sub 20/TPP)Fe/sup III/Cl represents the most electron-deficient iron(III) porphyrin which has been examined. The authors findings include the observations that a large portion of DA oxidation occurs prior to the diffusion apart of DA and ((/sup +/F/sub 20/TPP)Fe/sup IV/O)Cl. Also, they find that within the solvent cage/((/sup +/F/sub 20/TPP)Fe/sup IV/O)Cl x DA/ the two reactions of hydroxylation of the aromatic ring of DA (a feature not previously observed in the reaction of NO with other substituted tetraphenylporphyrins) and demethylation of DA compete equally. After dissociation of /((/sup +/F/sub 20/TPP)Fe/sup IV/O)Cl x DA/ the biomolecular reaction of the components ((/sup +/F/sub 20/TPP)Fe/sup IV/O)Cl + DA results only in the demethylation of DA.
Research Organization:
Univ. of California, Santa Barbara
OSTI ID:
6368183
Journal Information:
J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:11; ISSN JACSA
Country of Publication:
United States
Language:
English