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Titolo:
"Intermolecular" trapping of a nonheme Fe(IV)=O intermediate
Autore:
Miyake, H; Chen, K; Lange, SJ; Que, L;
Indirizzi:
Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA Univ Minnesota Minneapolis MN USA 55455 t Chem, Minneapolis, MN 55455 USA Univ Minnesota, Ctr Met Biocatalysis, Minneapolis, MN 55455 USA Univ Minnesota Minneapolis MN USA 55455 alysis, Minneapolis, MN 55455 USA
Titolo Testata:
INORGANIC CHEMISTRY
fascicolo: 14, volume: 40, anno: 2001,
pagine: 3534 - 3538
SICI:
0020-1669(20010702)40:14<3534:"TOANF>2.0.ZU;2-S
Fonte:
ISI
Lingua:
ENG
Soggetto:
ALKANE FUNCTIONALIZATION; DIOXYGEN ACTIVATION; HYDROXYLATION; ENZYMES; COMPLEXES; OXIDATION; CENTERS;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
20
Recensione:
Indirizzi per estratti:
Indirizzo: Que, L Univ Minnesota, Dept Chem, 207 Pleasant St SE, Minneapolis, MN 55455 USA Univ Minnesota 207 Pleasant St SE Minneapolis MN USA 55455 5455 USA
Citazione:
H. Miyake et al., ""Intermolecular" trapping of a nonheme Fe(IV)=O intermediate", INORG CHEM, 40(14), 2001, pp. 3534-3538

Abstract

The reactions of Fe-III(TPA) (TPA = tris(2-pyridylmethyl)amine) complexes with 2-methyl-1-phenyl-2-propyl-hydroperoxide (MPPH) delivered by syringe pump under anaerobic conditions afford nearly quantitative conversion of MPPH to products derived from the benzyl radical. These results unequivocally show that MPPH breaks down by O-O bond homolysis, leading to the formation of the benzyl radical and a high valent Fe(IV)=O species. Without added substrates, the benzyl radical reacts with the high valent species to form benzyl alcohol or benzyl halides. The Fe(IV)=O species can also effect the two-electron oxidation of added substrates such as thioanisole, cyclohexanol, and cyclooctene under appropriate conditions. The oxidation of thioanisole and cyclohexanol is likely facilitated by pre-equilibrium binding of the substrate to the metal center, allowing these substrates to intercept the high valent iron-oxo species as it forms. These results suggest the importanceof close proximity to direct the high valent metal center down a desired pathway.

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Documento generato il 29/03/20 alle ore 14:48:19