Chemical Plausibility of Cu(III) with Biological Ligation in pMMO

Autor:	Cooper Citek, J. Brannon Gary, T. Daniel P. Stack, Erik C. Wasinger
Rok vydání:	2015
Předmět:	biology Methane monooxygenase chemistry.chemical_element Active site General Chemistry Photochemistry Biochemistry Combinatorial chemistry Copper Redox Catalysis Colloid and Surface Chemistry chemistry Oxygenases biology.protein Thermodynamics Chemical stability
Zdroj:	Journal of the American Chemical Society. 137:6991-6994
ISSN:	1520-5126 0002-7863
Popis:	The mechanisms of dioxygen activation and methane C-H oxidation in particulate methane monooxygenase (pMMO) are currently unknown. Recent studies support a binuclear copper site as the catalytic center. We report the low-temperature assembly of a high-valent dicopper(III) bis(μ-oxide) complex bearing marked structural fidelity to the proposed active site of pMMO. This unprecedented dioxygen-bonded Cu(III) species with exclusive biological ligation directly informs on the chemical plausibility and thermodynamic stability of the bis(μ-oxide) structure in such dicopper sites and foretells unusual optical signatures of an oxygenation product in pMMO. Though the ultimate pMMO active oxidant is still debated, C-H oxidation of exogenous substrates is observed with the reported Cu(III) complexes. The assembly of a high valent species both narrows the search for relevant pMMO intermediates and provides evidence to substantiate the role of Cu(III) in biological redox processes.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::a55d1345058e5cb11657b301ede409be https://doi.org/10.1021/jacs.5b02157 Zobrazit plný text záznamu