Abstract
The monohydroxo-bridged dicopper(II) complex (1), its reduced dicopper(I) analogue (2) and the trans-μ-1,2-peroxo-dicopper(II) adduct (3) with the macrocyclic N-donor ligand [22]py4pz (9,22-bis(pyridin-2′-ylmethyl)-1,4,9,14,17,22,27,28,29,30- decaazapentacyclo -[22.2.114,7.111,14.117,20]triacontane-5,7(28),11(29),12,18,20(30), 24(27),25-octaene), have been prepared and characterized, including a 3D structure of 1 and 2. These compounds represent models of the three states of the catechol oxidase active site: met, deoxy (reduced) and oxy. The dicopper(II) complex 1 catalyzes the oxidation of catechol model substrates in aerobic conditions, while in the absence of dioxygen a stoichiometric oxidation takes place, leading to the formation of quinone and the respective dicopper(I) complex. The catalytic reaction follows a Michaelis–Menten behavior. The dicopper(I) complex binds molecular dioxygen at low temperature, forming a trans-μ-1,2-peroxo-dicopper adduct, which was characterized by UV–Vis and resonance Raman spectroscopy and electrochemically. This peroxo complex stoichiometrically oxidizes a second molecule of catechol in the absence of dioxygen. A catalytic mechanism of catechol oxidation by 1 has been proposed, and its relevance to the mechanisms earlier proposed for the natural enzyme and other copper complexes is discussed.
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Acknowledgements
Support of the NRSC Catalysis (a Research School Combination of HRSMC and NIOK) is kindly acknowledged. Also support and sponsorship concerted by COST Action D21/003/2001 is gratefully acknowledged. Collaborative travel grant from the French Ministry of Research and Foreign Affairs (EGIDE) and NWO (Van Gogh Programme), allowing visits and exchanges between Leiden and Grenoble, is gratefully acknowledged. We are very much indebted to Prof. L. Casella and Dr. E. Monzani (University of Pavia, Italy) for their kind assistance with the monophenolase activity studies and for hosting one of the co-authors (AMS). Crystallographic data (without structure factors) for the structure of 2 reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-269469. Copies of the data can be obtained free of charge from the CCDC (12 Union Road, Cambridge CB2 1EZ, UK; tel: (+44) 1223-336-408; fax: (+44) 1223-336-003; e-mail: deposit@ccdc.cam.ac.uk; website see link below).
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Koval, I.A., Belle, C., Selmeczi, K. et al. Catecholase activity of a μ-hydroxodicopper(II) macrocyclic complex: structures, intermediates and reaction mechanism. J Biol Inorg Chem 10, 739–750 (2005). https://doi.org/10.1007/s00775-005-0016-2
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DOI: https://doi.org/10.1007/s00775-005-0016-2