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Synthesis and Catalytic Reactivity of a Dicopper(II) μ‑η22‑Peroxo Species Supported by 1,4,7-Tri-tert-butyl-1,4,7-triazacyclononane

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posted on 01.02.2016, 00:00 by Gregory J. Karahalis, Arumugam Thangavel, Bryant Chica, John Bacsa, R. Brian Dyer, Christopher C. Scarborough
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-triazacyclononane) supports a dicopper­(II) μ-η22-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.