H 2 O Activation for Hydrogen‐Atom Transfer: Correct Structures and Revised Mechanisms | Zendy

Gansäuer Andreas | Zendy; Behlendorf Maike | Zendy; Cangönül Asli | Zendy; Kube Christian | Zendy; Cuerva Juan M. | Zendy; Friedrich Joachim | Zendy; van Gastel Maurice | Zendy

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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.

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