The aerobic chemistry of copper in biology and synthetic systems is remarkably rich. Dioxygen activation by copper provides species capable of oxidizing substrates ranging in reactivity from phenol to methane. While the past decade has seen an explosion in our understanding of the electronic structures of copper-dioxygen species, exploitation of these highly reactive intermediates in catalysis has not been fully realized, largely owing to oxidative susceptibility of supporting ligands. In this contribution, the dioxygen reactivity of copper ions enabled by 1,4,7-triazaclcylononane (tacn) ligands bearing tertiary alkyl nitrogen substituents will be described. These ligands do not suffer from the typical decomposition pathway, oxidative N-dealkylation, enabling exploration of intermolecular reactivity, the details of which will be the subject of this talk.

Aerobic copper chemistry supported by the bulkiest triazacyclononane derivatives

248th National Meeting (2014)

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