Inorganic Chemistry
Communication
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Quantum Refinement Does Not Support Dinuclear Copper Sites in
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oxygenase Contains Only Mononuclear Copper Centers. Science
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slowly and performs strong C−H oxidation reactions, which
could potentially shed light on the involvement of such high-
valent reactive species in the catalytic cycle of copper
monooxygenases. Further research involving the effects of
the coordination environment and geometry of the LCuI
systems on the oxidation rates and product yields is ongoing.
ASSOCIATED CONTENT
* Supporting Information
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The Supporting Information is available free of charge on the
Synthetic and analytical details (methodologies, 1H
NMR, and UV−vis spectra) (PDF)
(6) Hedegård, E. D.; Ryde, U. Multiscale Modelling of Lytic
Polysaccharide Monooxygenases. ACS Omega 2017, 2, 536−545.
(7) (a) Wang, B.; Walton, P. H.; Rovira, C. Molecular Mechanisms
of Oxygen Activation and Hydrogen Peroxide Formation in Lytic
Polysaccharide Monooxygenases. ACS Catal. 2019, 9, 4958−4969.
(b) Caldararu, O.; Oksanen, E.; Ryde, U.; Hedegård, E. D.
Mechanism of Hydrogen Peroxide Formation by Lytic Polysaccharide
Monooxygenase. Chem. Sci. 2019, 10, 576−586. (c) Hangasky, J. A.;
Detomasi, T. C.; Marletta, M. A. Glycosidic Bond Hydroxylation by
Polysaccharide Monooxygenases. Trends Chem. 2019, 1, 198−209.
AUTHOR INFORMATION
Corresponding Author
ORCID
Notes
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(8) (a) Schroder, D.; Holthausen, M. C.; Schwarz, H. Radical-Like
The authors declare no competing financial interest.
Activation of Alkanes by the Ligated Copper Oxide Cation
(Phenanthroline)CuO+. J. Phys. Chem. B 2004, 108, 14407−14416.
(b) Dietl, N.; Schlangen, M.; Schwarz, H. Thermal Hydrogen-Atom
Transfer from Methane: The Role of Radicals and Spin States in Oxo-
Cluster Chemistry. Angew. Chem., Int. Ed. 2012, 51, 5544−5555.
ACKNOWLEDGMENTS
Research support of the National Institutes of Health (Grant
GM 28962) is gratefully acknowledged. D.E.D. thanks the
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Comision Nacional de Investigacion Cientifica y Tecnologica
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(c) Rijs, N. J.; Gonzalez-Navarrete, P.; Schlangen, M.; Schwarz, H.
(CONICYT) for a Becas Chile Scholarship (Code 72110038).
Penetrating the Elusive Mechanism of Copper-Mediated Fluorome-
thylation in the Presence of Oxygen through the Gas-Phase Reactivity
of Well-Defined [LCuO]+ Complexes with Fluoromethanes
(CH(4‑n)Fn, n = 1−3). J. Am. Chem. Soc. 2016, 138, 3125−3135.
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