Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 55, Issue 35, Pages 10453-10457Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201605159
Keywords
coordination chemistry; copper dioxygen; extreme solution temperatures; N tau imidazole ligation
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Funding
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-76SF00515]
- DOE Office of Biological and Environmental Research
- National Institutes of Health, National Institute of General Medical Sciences [P41GM103393]
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Tyrosinases are ubiquitous binuclear copper enzymes that oxygenate to (Cu2O2)-O-II cores bonded by three histidine N tau-imidazoles per Cu center. Synthetic monodentate imidazole-bonded (Cu2O2)-O-II species self-assemble in a near quantitative manner at -125 degrees C, but N pi-ligation has been required. Herein, we disclose the syntheses and reactivity of three N tau-imidazole bonded (Cu2O2)-O-II species at solution temperatures of -145 degrees C, which was achieved using a eutectic mixture of THF and 2-MeTHF. The addition of anionic phenolates affords a (Cu2O2)-O-III species, where the bonded phenolates hydroxylate to catecholates in high yields. Similar (Cu2O2)-O-III intermediates are not observed using N pi-bonded (Cu2O2)-O-II species, hinting that Nt-imidazole ligation, conserved in all characterized Ty, has functional advantage beyond active-site flexibility. Substrate accessibility to the oxygenated Cu2O2 core and stabilization of a high oxidation state of the copper centers are suggested from these minimalistic models.
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