The formation and reactivity of {Cun-O2} moieties are of interest to the scientific community for understanding both industrial and biological oxidation chemistry. A Cu(I) fully fluorinated O-donor monodentate alkoxide complex, K[Cu(OC4F9)2], was previously shown to form a trinuclear copper-dioxygen species with a {Cu3(μ3-O)2}3- core, TOC4F9, upon reactivity with O2 at low temperature. More recently, a bidentate counter-part with the perfluoropinacolate (pinF) ligand was synthesized, K[Cu(pinF)(PR3)], and found to also form a {Cu3(μ3-O)2}3- core, TpinF, when exposed to O2. Both T cores were characterized by resonance Raman, EPR, and cold-spray ionization mass spectroscopies. The kinetics of formation of both complexes were recently evaluated using low temperature stopped-flow, permitting the detection of intermediates along the formation pathways. Both T cores were also evaluated for both oxidase and oxygenase substrate reactivity. The results of these formation and reactivity studies will be compared to one another and the other species in the literature.

Formation, spectroscopy, and oxidase/oxygenase reactivity of two fluorinated {Cu3O2} species

256th National Meeting (2018)

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