Synthesis and Catalytic Reactivity of a Dicopper(II) μ-η2:η2-Peroxo Species Supported by 1,4,7-Tri-tert-butyl-1,4,7-triazacyclononane
O2-derived CunO2 adducts are attractive targets for aerobic oxidation
catalysis because of their remarkable reactivity, but oxidation of the supporting ligand
limits catalytic turnover. We report that tBu3tacn (1,4,7-tri-tert-butyl-1,4,7-triazacyclo-
nonane) supports a dicopper(II) μ-η2:η2-peroxo species with the highest solution
stability outside of an enzyme. Decomposition of this species proceeds without oxidation
of the tBu3tacn ligand. Additive-free catalytic aerobic oxidation reactions at or above
room temperature are described, highlighting the potential of oxidatively robust ligands
in aerobic copper catalysis.
Inorganic Chemistry
DOI: 10.1021/acs.inorgchem.5b02205
They reported the crystal structure of dinuclear copper(II)-side on peroxide complex supported by tBu3tacn ligand. This species gave the highest stability among the dicopper(II) peroxide complexes (t1/2 = 9.6 days in aqueous Na2HPO4) due to the lack of the active C–H bond. Catalytic reactivity has also examined for the first time, taking the opportunity of the high stability.
The reactivity of this species is not so much attractive, however, the high stability and selective formation of such an active oxygen species is impressive.
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