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Dioxygen reactivity of new models of copper oxygenases : electrochemical and spectroscopic studies

Abstract : Methane has the strongest C-H bond of any hydrocarbon (BDE = 104 kcal mol-1); its oxidation under mild conditions remains a great challenge. The particulate Methane Monooxygenase (pMMO) is a copper enzyme that oxides methane (CH4) to methanol (CH3OH). In the active site of the enzyme, two copper ions are located at a short distance (2.6 Å). Recent researches have suggested a mixed-valent Cu2III,II/O2 cluster as a key intermediate in the catalytic cycle. The main objective of this work was the synthesis and characterization of new mixed-valent CuIIICuII bis(μ-oxo) and (μ-OH, μ-O) dinuclear complexes. For this purpose we designed promising symmetrical and unsymmetrical complexes based on specific and distinct scaffolds for each side of the structure. Two families of coordination pattern have been used, polypyridyle or polyamide; the two sites are shortly and rigidly bridged by phenoxo, alkoxo or naphthyridine linkers. New complexes have been characterized by electrochemistry, UV-vis and EPR spectroscopies, and by theoretical calculations. A new cryo-UV-Vis-NIR spectroelectrochemical set up, developed in parallel during this work, has allowed the spectroscopic identification of these transient intermediate species, known to be unstable at room temperature. New mixed-valence Cu2 III,II(μ-OH, μ-O) and Cu2 III,IIbis(μ-OH) complexes have been characterized. These results expand the recent knowledge on the only mixed valent CuIII(μ-OH)CuII species described so far.
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Submitted on : Monday, June 18, 2018 - 9:59:14 AM
Last modification on : Wednesday, October 14, 2020 - 3:52:14 AM
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  • HAL Id : tel-01817527, version 1


Federica Gennarini. Dioxygen reactivity of new models of copper oxygenases : electrochemical and spectroscopic studies. Other. Université de Bretagne occidentale - Brest, 2017. English. ⟨NNT : 2017BRES0108⟩. ⟨tel-01817527⟩



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