Copper-dioxygen chemistry has proven to be a rich field of study for both the inorganic and bioinorganic communities, in part due to the biochemically convenient Cu(I/II) redox couple and the high bioavailability of copper.A commonly invoked 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 understood to perform hydrogen atom abstractionto initiate substratefunctionalization. As a result, there is notable interest within the inorganic chemistry community in isolating end-on cupric superoxide model complexes and studying their reactivity. This talk describesa seriesof end-on cupric superoxide complexes bound by novel tren-based,tris(phosphinimine) ligands. The thermal decomposition of these complexes has been studied, and two unique pathways have been identified. One thermal product is found to perform net hydrogen atom abstraction from organic substrates. An observed pK<sub>a</sub>dependence on substrate reactivity implicates the Brønsted-basic phosphiniminato substituents of the ligand as being involved in a sequentialPT-ET-type mechanism.

Copper-dioxygen chemistry using novel tren-based, tris(phosphinimine) ligands

2019 Fall National Meeting

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