テトラメチル→ジメチル→メチル基なしでビスmオキソの安定性が変わり、配位子交換がおこるそうです。
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† Department of Chemistry, Stanford University, Stanford, California 94305, United States
‡ Department of Chemistry and Biochemistry, California State University, Chico, California 95929, United States
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/ja508630d
Publication Date (Web): September 30, 2014
Copyright © 2014 American Chemical Society
Abstract
Here we report the formation of the first examples of dicopper(III) bis(μ-oxo) complexes ligated by the primary amines, propylenediamine, and N,N,-dimethyl propylenediamine. Stabilization of these new compounds is effected at −125 °C by “core capture”— introduction of exogenous ligand to a preformed dicopper(III) bis(μ-oxo) complex supported by the peralkylated tetramethyl propylenediamine. Primary amine ligation in these compounds matches the single primary amine coordination of the putative active site of particulate methane monooxygenase (pMMO) and polysaccharide monooxygenase. Reactivity studies presented here show primary amine ligated cores are competent oxidants, capable of activating C–H bonds by an H-atom abstraction mechanism. Trends in spectroscopy, structure, and reactivity provide hints to the potential role of primary amine ligation in pMMO: increased substrate accessibility to the redox active orbitals of the Cu2O2 core and greater stabilization of the oxidant without attenuation of oxidizing power.
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