Comparison of FeIV=O heme and non-heme species:: Electronic structures, bonding, and reactivities

被引：61

作者：

Decker, A ^{[1
]}

Solomon, EI ^{[1
]}

机构：

[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2005年 / 44卷 / 15期

关键词：

bioinorganic chemistry; density functional calculations; electronic structure; high-valent compounds; iron;

D O I：

10.1002/anie.200462182

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Chemical Equation Presented) Extremely similar electronic structures and Fe-O bonding characterize FeIV=O S = 1 heme and non-heme species as a result of a decoupling of the oxoiron unit from the porphyrin (Por) π system in the heme complex (see scheme). However, along the reaction coordinate towards an FeIII-OH product, the Por π system interacts with the iron d orbitals, thus resulting in different reactivities for heme and non-heme complexes. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：2252 / 2255

页数：4

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