Hydrogen atom abstraction reactivity of biomimetic distorted dicopper(III) bis(μ-oxo) complexes
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Date
2019-12
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The Ohio State University
Abstract
With diminishing liquid petroleum resources, methane has become an important component in supporting our continued need for hydrocarbons and their derived products. The enzyme particulate methane monooxygenase (pMMO) can perform the important methane to methanol conversion at ambient conditions, however we have little mechanistic understanding how this enzyme performs the reaction. pMMO and other C-H bond activating enzymes contain unsymmetrical dicopper-oxygen active sites. Many models studies have been performed to examine the reactivity of these moieties, yet few if any have specifically examined the effect of the unsymmetrical feature on reactivity. To examine this feature, we prepared two synthetic dicopper(III) bis(μ-oxo) model compounds with differing degrees of geometric distortion. The reactivity of the models was tested with C-H bond substrates, and it was determined that the model with a greater degree of predicted geometric distortion had significantly higher C-H abstraction reactivity. The preliminary knowledge gained from this study—that distortion can increase reactivity—can be applied to current thinking about dicopper-oxygen active site function.
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Keywords
Bioinorganic, Metalloproteins, Synthesis, Reactivity, Chemistry