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Issue 27, 2016
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Supramolecular control of monooxygenase reactivity in a copper(ii) cryptate

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We report a detailed investigation of the formation and self-decomposition of Cu(II)–hydroperoxo intermediates under the influence of second-coordination-sphere features provided by a cryptand. In solution, an equilibrium between two copper complexes with square-planar and square-pyramidal geometries was identified. Upon addition of H2O2/Et3N, two copper(II)–hydroperoxo intermediates formed at different rates. Their decomposition via self-oxidation was probed by deuterating select positions on the cryptand. This led to a small kinetic isotope effect of 1.5. Mass spectrometry analysis of the demetallated organic products is consistent with a direct oxygen-atom transfer to a tertiary amine on the cryptand, forming an N-oxide, unlike other models of copper mononuclear monooxygenase enzymes.

Graphical abstract: Supramolecular control of monooxygenase reactivity in a copper(ii) cryptate

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Article information

03 Feb 2016
13 Jun 2016
First published
13 Jun 2016

Dalton Trans., 2016,45, 11109-11119
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Author version available

Supramolecular control of monooxygenase reactivity in a copper(II) cryptate

L. Chaloner, A. Khomutovskaya, F. Thomas and X. Ottenwaelder, Dalton Trans., 2016, 45, 11109
DOI: 10.1039/C6DT00490C

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