Aerobic copper chemistry is a rich field with a wide variety of oxidative reactivity. Unfortunately, the potential of oxidative catalysis by well-defined copper-dioxygen species has been limited owing to oxidation of the supporting ligand by these inherently reactive moieties. This tendency has precluded the use of certain ligand platforms for catalysis, including N-substituted derivatives of 1,4,7-triazacyclononane (tacn).  However, recently published tacn ligands with tertiary alkyl nitrogen substituents (e.g. tBu-3tacn) are uniquely stable to oxidative decomposition by copper-dioxygen adducts, opening the door to the investigation of not only the properties of copper-oxygen species with unprecedented stability, but also the substrate scope of these species.  This contribution will describe both electrochemical properties and substrate scope of a Cu2(O2) species supported by two tBu3tacn ligands, emphasizing both stoichiometric and catalytic oxidation of substrates with various functional groups, including ethers, amines, and phenols.

Exploration of copper-dioxygen species with unprecedented stability

248th National Meeting (2014)

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