Dual oxidase/oxygenase reactivity and resonance Raman spectra of {Cu3O2} moiety with perfluoro-: T -butoxide ligands

Journal article


Publication Details

Author(s): 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
Journal: Dalton Transactions
Publication year: 2019
Volume: 48
Journal issue: 20
Pages range: 6899-6909
ISSN: 1477-9226
eISSN: 1477-9234


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

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.


FAU Authors / FAU Editors

Ivanovic-Burmazovic, Ivana Prof. Dr.
Lehrstuhl für Bioanorganische Chemie
Orth, Nicole
Lehrstuhl für Bioanorganische Chemie


External institutions with authors

Boston University
Rheinisch-Westfälische Technische Hochschule (RWTH) Aachen
Universität Hamburg


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.

BibTeX: 

Last updated on 2019-06-08 at 09:18