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

In contradiction to what has been postulated before, the formation of cationic hydrated TiIII complexes is crucial for the activation of H2O towards hydrogen‐atom transfer (HAT). The relevant intermediates have been characterized by modern EPR methods (see spectrum) and cyclic voltammetry. The struc...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2012-03, Vol.51 (13), p.3266-3270
Main Authors: Gansäuer, Andreas, Behlendorf, Maike, Cangönül, Asli, Kube, Christian, Cuerva, Juan M., Friedrich, Joachim, van Gastel, Maurice
Format: Article
Language:English
Subjects:
EPR spectroscopy
hydrogen-atom transfer
radicals
titanium
water
Online Access:Get full text
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Summary:In contradiction to what has been postulated before, the formation of cationic hydrated TiIII complexes is crucial for the activation of H2O 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.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201107556