H2O Activation for Hydrogen-Atom Transfer: Correct Structures and Revised Mechanisms

被引：69

作者：

Gansaeuer, Andreas ^{[1
]}

Behlendorf, Maike ^{[1
]}

Cangoenuel, Asli ^{[4
]}

Kube, Christian ^{[1
]}

Cuerva, Juan M. ^{[3
]}

Friedrich, Joachim ^{[2
]}

van Gastel, Maurice ^{[4
]}

机构：

[1] Univ Bonn, Kekul Inst Organ Chem & Biochem, D-53121 Bonn, Germany

[2] Tech Univ Chemnitz, Inst Chem, D-09111 Chemnitz, Germany

[3] Univ Granada, Fac Sci, Dept Organ Chem, E-18071 Granada, Spain

[4] Univ Bonn, Inst Phys & Theoret Chem, D-53115 Bonn, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2012年 / 51卷 / 13期

关键词：

EPR spectroscopy; hydrogen-atom transfer; radicals; titanium; water; ELECTRON-SPIN-RESONANCE; TI-III; CORRELATION-ENERGY; WATER; COMPLEXES; APPROXIMATION; SPECTROSCOPY; REDUCTION; EXCHANGE; BORANE;

D O I：

10.1002/anie.201107556

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

In contradiction to what has been postulated before, the formation of cationic hydrated Ti III complexes is crucial for the activation of H 2O towards hydrogen-atom transfer (HAT). The relevant intermediates have been characterized by modern EPR methods (see spectrum) and cyclic voltammetry. The structural assignments were verified by a comprehensive computational study. The calculated bond dissociation energies are in agreement with a previous kinetic investigation. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：3266 / 3270

页数：5

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