Dual oxidase/oxygenase reactivity and resonance Raman spectra of {Cu3O2} moiety with perfluoro-t-butoxide ligands. Issue 20 (30th April 2019)

• Record Type: Journal Article
• Authors: Brazeau, Sarah E. N.; Norwine, Emily E.; Hannigan, Steven F.; Orth, Nicole; Ivanović-Burmazović, Ivana; Rukser, Dieter; Biebl, Florian; Grimm-Lebsanft, Benjamin; Praedel, Gregor; Teubner, Melissa; Rübhausen, Michael; Liebhäuser, Patricia; Rösener, Thomas; Stanek, Julia; Hoffmann, Alexander; Herres-Pawlis, Sonja; Doerrer, Linda H.
• Is Part Of: Dalton transactions. Volume 48:Issue 20(2019)
• Page Start: 6899
• Page End: 6909
• Publication Date: 2019-04-30
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/c9dt00516a
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : A mechanism for the formation of O-donor trinuclear {Cu3 O2 } moiety is reported. Abstract : A Cu(i ) fully fluorinated O-donor monodentate alkoxide complex, K[Cu(OC4 F9 )2 ], was previously shown to form a trinuclear copper–dioxygen species with a {Cu3 (μ3 -O)2 } core, T OC 4 F 9, upon reactivity with O2 at low temperature. Herein is reported a significantly expanded kinetic and mechanistic study ofT OC 4 F 9 formation using stopped-flow spectroscopy. TheT OC 4 F 9 complex performs catalytic oxidase conversion of hydroquinone (H2 Q) to benzoquinone (Q).T OC 4 F 9 also demonstrated hydroxylation of 2, 4-di- tert -butylphenolate (DBP) to catecholate, makingT OC 4 F 9 the first trinuclear species to perform tyrosinase (both monooxygenase and oxidase) chemistry. Resonance Raman spectra were also obtained forT OC 4 F 9, to our knowledge, the first such spectra for anyT species. The mechanism and substrate reactivity ofT OC 4 F 9 are compared to those of its bidentate counterpart, T pin F, formed from K[Cu(pin F )(PR3 )]. The monodentate derivative has both faster initial formation and more diverse substrate reactivity.