Many natural metalloenzymes employ copper in their active sites and include copper-oxygen intermediates within catalytic cycles that initiate difficult substrate transformations, such as oxidation or oxygenations of O-H, N-H, and C-H bonds. A commonly invoked copper-dioxygen intermediate in copper-containing oxidases (galactose oxidase, copper amine oxidase) and oxygenases (peptiglycine alpha-hydroxylating monooxygenase, dopamine β-monooxygenase, tyramine β-monooxygenase) is the cupric superoxide, which is generally proposed to perform hydrogen atom abstractions to activate substrates. As a result, there is notable interest within the inorganic chemistry community in isolating end-on cupric superoxide model complexes, and studying their reactivity. We recently reported a novel class of cupric superoxide complexes that show relatively high thermal stability. Herein, we report the catalytic activity of tris(phosphinimine)-bound copper(I) complexes in aerobic oxidation and oxygenation reactions of alcoholic and phenolic substrates respectively. Stoichiometric reactivity of phenols with tris(phosphinimine)-bound cupric superoxide complexes and tris(phosphinimine)-bound copper(II) hydroxide complexes will be presented and evaluated for being active species in these catalytic transformations. Furthermore, the tris(phosphinimine) ligand framework provides a high degree of tunability of the Cu(I)/Cu(II) redox couple and steric bulk in the secondary coordination sphere, which can be varied to affect reactivity in a systematic way.

Synthetic copper(II) complexes evaluated as active species in oxygenation catalysis

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.