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Experimental and theoretical evidence for nonheme iron (III) alkylperoxo species as sluggish oxidants in oxygenation reactions
被引:59
|作者:
Seo, Mi Sook
Kamachi, Takashi
Kouno, Tomohisa
Murata, Koji
Park, Mi Joo
Yoshizawa, Kazunari
[1
]
Nam, Wonwoo
机构:
[1] Kyushu Univ, Inst Mat Chem & Engn, Fukuoka 8128581, Japan
[2] Ewha Womans Univ, Dept Chem, Div Nanosci, Seoul 120750, South Korea
[3] Ewha Womans Univ, Dept Chem, Ctr Biomimet Syst, Seoul 120750, South Korea
关键词:
density functional calculations;
enzyme models;
iron;
oxo ligands;
oxygenation;
D O I:
10.1002/anie.200604219
中图分类号:
O6 [化学];
学科分类号:
0703 ;
摘要:
The active oxidant that oxygenates organic substrates is an iron(IV) oxo intermediate, namely, [(tpa)FeIV(O)(CH3CN)]2+ (2), which is formed through O-O bond homolysis, according to experimental and computational studies on the reactivity of nonheme iron(III) alkylperoxo complex [(tpa)FeIII(OOtBu)(CH3CN)]2+ (1), which was shown to be a sluggish electrophilic oxidant that is incapable of oxygenating organic substrates. tpa = tris(2-pyridylmethyl)amine. (Chemical Equation Presented). © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.
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页码:2291 / 2294
页数:4
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