Dual oxidase/oxygenase reactivity and resonance Raman spectra of {Cu3O2} moiety with perfluoro-: T -butoxide ligands
Brazeau SE, Norwine EE, Hannigan SF, Orth N, Ivanovic-Burmazovic I, Rukser D, Biebl F, Grimm-Lebsanft B, Praedel G, Teubner M, Rübhausen M, Liebhäuser P, Rösener T, Stanek J, Hoffmann A, Herres-Pawlis S, Doerrer LH (2019)
Publication Type: Journal article
Publication year: 2019
Journal
Book Volume: 48
Pages Range: 6899-6909
Journal Issue: 20
DOI: 10.1039/c9dt00516a
Abstract
A 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 OC 4 F 9 , upon reactivity with O 2 at low temperature. Herein is reported a significantly expanded kinetic and mechanistic study of T OC 4 F 9 formation using stopped-flow spectroscopy. The T OC 4 F 9 complex performs catalytic oxidase conversion of hydroquinone (H 2 Q) to benzoquinone (Q). T OC 4 F 9 also demonstrated hydroxylation of 2,4-di-tert-butylphenolate (DBP) to catecholate, making T OC 4 F 9 the first trinuclear species to perform tyrosinase (both monooxygenase and oxidase) chemistry. Resonance Raman spectra were also obtained for T OC 4 F 9 , to our knowledge, the first such spectra for any T species. The mechanism and substrate reactivity of T OC 4 F 9 are compared to those of its bidentate counterpart, T pin F , formed from K[Cu(pin F )(PR 3 )]. The monodentate derivative has both faster initial formation and more diverse substrate reactivity.
Authors with CRIS profile
Nicole Orth
Lehrstuhl für Bioanorganische Chemie
Ivana Ivanovic-Burmazovic
Lehrstuhl für Bioanorganische Chemie
Involved external institutions
Rheinisch-Westfälische Technische Hochschule (RWTH) Aachen
Germany (DE)
Universität Hamburg (UHH)
Germany (DE)
Boston University
United States (USA) (US)
Germany (DE)
Universität Hamburg (UHH)
Germany (DE)
Boston University
United States (USA) (US)
How to cite
APA:
Brazeau, S.E., Norwine, E.E., Hannigan, S.F., Orth, N., Ivanovic-Burmazovic, I., Rukser, D.,... Doerrer, L.H. (2019). Dual oxidase/oxygenase reactivity and resonance Raman spectra of {Cu3O2} moiety with perfluoro-: T -butoxide ligands. Dalton Transactions, 48(20), 6899-6909. https://dx.doi.org/10.1039/c9dt00516a
MLA:
Brazeau, Sarah E.N., et al. "Dual oxidase/oxygenase reactivity and resonance Raman spectra of {Cu3O2} moiety with perfluoro-: T -butoxide ligands." Dalton Transactions 48.20 (2019): 6899-6909.
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