Amanda Arnoff (Class of ’17)
CuI complexes of the form K[(R3P)Cu(pinF)], in which (pinF)2− is the bidentate, oxygen‐donating ligand perfluoropinacolate, were synthesized and characterized. Low‐temperature oxygenation of the K[(R3P)Cu(pinF)(PR3)] species resulted in a trisanionic bis(μ3‐oxo) trinuclear copper(II,II,III) core characterized by UV/Vis spectroscopy (λmax [nm] = 330, 535, 630), cryospray‐ionization mass spectrometry, and X‐band electron paramagnetic resonance spectroscopy (derivative resonance at 3300 G, Δms=2 at 1500 G). The kinetic behavior of the trimeric {Cu3O2} species was quantified by stopped‐flow spectroscopy and the associated electronic structures were investigated by DFT calculations. An asymmetric {Cu3O2} species, AsTpinF, which bears a structure similar to multicopper oxidases, forms prior to full formation of the symmetric trinuclear core, SyTpinF. The trimer catalytically oxidizes para‐hydroquinone to benzoquinone (a form of oxidase chemistry).