Mononuclear and Dinuclear Copper Complexes of Tridentate Redox-active Ligands with Tunable H-bonding Donors: Structure,Spectroscopy and H+/e− Reactivity |
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Authors: | Tong Wu Justin Musgrove Maxime A Siegler Dr Isaac Garcia-Bosch |
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Institution: | 1. Department of Chemistry, Southern Methodist University, Dallas, Texas, 75275 United States;2. Department of Chemistry, Johns Hopkins University, Baltimore, Maryland, 21218 United States |
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Abstract: | In this research article, we describe the synthesis and characterization of mononuclear and dinuclear Cu complexes bound by a family of tridentate redox-active ligands with tunable H-bonding donors. The mononuclear Cu-anion complexes were oxidized to the corresponding “high-valent” intermediates by oxidation of the redox-active ligand. These species were capable of oxidizing phenols with weak O−H bonds via H-atom abstraction. Thermodynamic analysis of the H-atom abstractions, which included reduction potential measurements, pKa determination and kinetic studies, revealed that modification of the anion coordinated to the Cu and changes in the H-bonding donor did not lead to major differences in the reactivity of the “high-valent” CuY complexes (Y: hydroxide, phenolate and acetate), which indicated that the tridentate ligand scaffold acts as the H+ and e− acceptor. |
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Keywords: | copper oxidations redox-active ligands H-atom abstraction Cu-monooxygenases |
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