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

共 34 条

[1] BALCH AL, 1984, J AM CHEM SOC, V106, P779
[2] Mechanism of aromatic hydroxylation by an activated feIV=O core in tetrahydrobiopterin-dependent hydroxylases
Bassan, A
Blomberg, MRA
Siegbahn, PEM
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2003, 9 (17) : 4055 - 4067
[3] Mechanism of dioxygen cleavage in tetrahydrobiopterin-dependent amino acid hydroxylases
Bassan, A
Blomberg, MRA
Siegbahn, PEM
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2003, 9 (01) : 106 - 115
[4] Mechanism of dioxygen activation in 2-oxoglutarate-dependent enzymes: A hybrid DFT study
Borowski, T
Bassan, A
Siegbahn, PEM
[J]. CHEMISTRY-A EUROPEAN JOURNAL, 2004, 10 (04) : 1031 - 1041
[5] Brune A, 2001, ELEC SOC S, V2000, P235
[6] X-RAY ABSORPTION STUDIES OF MYOGLOBIN PEROXIDE REVEAL FUNCTIONAL DIFFERENCES BETWEEN GLOBINS AND HEME ENZYMES
CHANCE, M
POWERS, L
KUMAR, C
CHANCE, B
[J]. BIOCHEMISTRY, 1986, 25 (06) : 1259 - 1265
[7] Dioxygen activation at mononuclear nonheme iron active sites: Enzymes, models, and intermediates
Costas, M
Mehn, MP
Jensen, MP
Que, L
[J]. CHEMICAL REVIEWS, 2004, 104 (02) : 939 - 986
[8] Resonance raman spectra of legitimate models for the ubiquitous compound I intermediates of oxidative heme enzymes
Czarnecki, K
Kincaid, JR
Fujii, H
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (34) : 7953 - 7954
[9] Spectroscopic and quantum chemical characterization of the electronic structure and bonding in a non-heme FeIV=O complex
Decker, A
Rohde, JU
Que, L
Solomon, EI
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (17) : 5378 - 5379
[10] True Iron(V) and Iron(VI) porphyrins: A first theoretical exploration
Dey, A
Ghosh, A
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (13) : 3206 - 3207

← 1 2 3 4 →