%ABrazeau, Sarah%ANorwine, Emily%AHannigan, Steven%AOrth, Nicole%AIvanović-Burmazović, Ivana%ARukser, Dieter%ABiebl, Florian%AGrimm-Lebsanft, Benjamin%APraedel, Gregor%ATeubner, Melissa%ARübhausen, Michael%ALiebhäuser, Patricia%ARösener, Thomas%AStanek, Julia%AHoffmann, Alexander%AHerres-Pawlis, Sonja%ADoerrer, Linda%BJournal Name: Dalton Transactions; Journal Volume: 48; Journal Issue: 20 %D2019%I %JJournal Name: Dalton Transactions; Journal Volume: 48; Journal Issue: 20 %K %MOSTI ID: 10097316 %PMedium: X %TDual oxidase/oxygenase reactivity and resonance Raman spectra of {Cu 3 O 2 } moiety with perfluoro- t -butoxide ligands %XA Cu( i ) fully fluorinated O-donor monodentate alkoxide complex, K[Cu(OC 4 F 9 ) 2 ], was previously shown to form a trinuclear copper–dioxygen species with a {Cu 3 (μ 3 -O) 2 } core, T OC4F9 , upon reactivity with O 2 at low temperature. Herein is reported a significantly expanded kinetic and mechanistic study of T OC4F9 formation using stopped-flow spectroscopy. The T OC4F9 complex performs catalytic oxidase conversion of hydroquinone (H 2 Q) to benzoquinone (Q). T OC4F9 also demonstrated hydroxylation of 2,4-di- tert -butylphenolate (DBP) to catecholate, making T OC4F9 the first trinuclear species to perform tyrosinase (both monooxygenase and oxidase) chemistry. Resonance Raman spectra were also obtained for T OC4F9 , to our knowledge, the first such spectra for any T species. The mechanism and substrate reactivity of T OC4F9 are compared to those of its bidentate counterpart, T pinF , formed from K[Cu(pin F )(PR 3 )]. The monodentate derivative has both faster initial formation and more diverse substrate reactivity. %0Journal Article