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Issue 20, 2019
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Dual oxidase/oxygenase reactivity and resonance Raman spectra of {Cu3O2} moiety with perfluoro-t-butoxide ligands

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Abstract

A Cu(I) fully fluorinated O-donor monodentate alkoxide complex, K[Cu(OC4F9)2], was previously shown to form a trinuclear copper–dioxygen species with a {Cu33-O)2} core, TOC4F9, upon reactivity with O2 at low temperature. Herein is reported a significantly expanded kinetic and mechanistic study of TOC4F9 formation using stopped-flow spectroscopy. The TOC4F9 complex performs catalytic oxidase conversion of hydroquinone (H2Q) to benzoquinone (Q). TOC4F9 also demonstrated hydroxylation of 2,4-di-tert-butylphenolate (DBP) to catecholate, making TOC4F9 the first trinuclear species to perform tyrosinase (both monooxygenase and oxidase) chemistry. Resonance Raman spectra were also obtained for TOC4F9, to our knowledge, the first such spectra for any T species. The mechanism and substrate reactivity of TOC4F9 are compared to those of its bidentate counterpart, TpinF, formed from K[Cu(pinF)(PR3)]. The monodentate derivative has both faster initial formation and more diverse substrate reactivity.

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

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Publication details

The article was received on 01 Feb 2019, accepted on 17 Apr 2019 and first published on 30 Apr 2019


Article type: Paper
DOI: 10.1039/C9DT00516A
Dalton Trans., 2019,48, 6899-6909

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

    S. E. N. Brazeau, E. E. Norwine, S. F. Hannigan, N. Orth, I. Ivanović-Burmazović, D. Rukser, F. Biebl, B. Grimm-Lebsanft, G. Praedel, M. Teubner, M. Rübhausen, P. Liebhäuser, T. Rösener, J. Stanek, A. Hoffmann, S. Herres-Pawlis and L. H. Doerrer, Dalton Trans., 2019, 48, 6899
    DOI: 10.1039/C9DT00516A

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