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H 2 O Activation for Hydrogen‐Atom Transfer: Correct Structures and Revised Mechanisms
Author(s) -
Gansäuer Andreas,
Behlendorf Maike,
Cangönül Asli,
Kube Christian,
Cuerva Juan M.,
Friedrich Joachim,
van Gastel Maurice
Publication year - 2012
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201107556
Subject(s) - chemistry , reagent , hydrogen atom , dissociation (chemistry) , carbene , bond dissociation energy , electron paramagnetic resonance , cyclic voltammetry , kinetic isotope effect , hydrogen bond , homoleptic , computational chemistry , crystallography , photochemistry , molecule , metal , deuterium , catalysis , alkyl , electrochemistry , organic chemistry , nuclear magnetic resonance , atomic physics , physics , electrode
In contradiction to what has been postulated before, the formation of cationic hydrated Ti III complexes is crucial for the activation of H 2 O 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.