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Title: Investigation of dioxygen activation by copper(ii)-iminate/aminate complexes
Authors: Papanikolaou, Michael G. 
Hadjithoma, Sofia 
Chatzikypraiou, Dimitra S. 
Papaioannou, Dionysios 
Drouza, Chryssoula 
Tsipis, Athanassios C. 
Miras, Haralampos N. 
Keramidas, Anastasios D. 
Kabanos, Themistoklis A. 
Major Field of Science: Natural Sciences
Field Category: Chemical Sciences
Keywords: Oxidation;Computation theory;Copper substrates;Metallo-proteins
Issue Date: 7-Dec-2018
Source: Dalton Transactions, 2018, vol. 47, no. 45, pp. 16242-16254
Volume: 47
Issue: 45
Start page: 16242
End page: 16254
Journal: Dalton Transactions 
Abstract: The activation of dioxygen by metal ions is critical in chemical and bio-chemical processes. A scientific challenge is the elucidation of the activation site of dioxygen in some copper metalloproteins, which is either the metal center or the substrate. In an effort to address this challenge, we prepared a series of new copper(ii) complexes (1·2H2O, 2·CH3OH, 3) with bio-inspired amidate ligands and investigated their activity towards dioxygen activation. The secondary amine group ligated to copper(ii) of the complex 1·2H2O in methyl alcohol is oxidized (2e-) by air dioxygen in a stepwise fashion to an imine group, affording complex 2. The copper(ii) complex 2 in methyl alcohol induces the 4e- oxidation by air dioxygen of the imine functionality ligated to copper(ii) to an azinate group, resulting in the isolation of a dinuclear azinate copper(ii) compound (4). Experimental and computational studies, including X-band c. w. EPR, UV-vis and ESI-MS spectroscopy and density functional theory computations, indicate a direct attack of the dioxygen on the -HC[double bond, length as m-dash]N- group ligated to copper(ii), and a possible mechanism of the oxidation of the -HC[double bond, length as m-dash]N- functionality ligated to copper(ii) to an azinate group is provided. This unprecedented activation of dioxygen by a copper substrate paves the way for further exploration of the O2 activation mechanisms in enzymes and the development of effective catalysts in O2-involved green organic synthesis.
ISSN: 1477-9226
DOI: 10.1039/c8dt03137a
Rights: © The Royal Society of Chemistry
Type: Article
Affiliation : University of Ioannina 
University of Cyprus 
University of Patras 
Cyprus University of Technology 
University of Glasgow 
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