Issue 15, 2019

Cu(i)–O2 oxidation reactions in a fluorinated all-O-donor ligand environment

Abstract

Investigation of Cu–O2 oxidation reactivity is important in biological and anthropogenic chemistry. Zeolites are one of the most promising Cu/O based oxidation catalysts for development of industrial-scale CH4 to CH3OH conversion. Their oxidation mechanisms are not well understood, however, highlighting the importance of the investigation of molecular Cu(I)–O2 reactivity with O-donor complexes. Herein, we give an overview of the synthesis, structural properties, and O2 reactivity of three different series of O-donor fluorinated Cu(I) alkoxides: K[Cu(OR)2], [(Ph3P)Cu(μ-OR)2Cu(PPh3)], and K[(R3P)Cu(pinF)], in which OR = fluorinated monodentate alkoxide ligands and pinF = perfluoropinacolate. This breadth allowed for the exploration of the influence of the denticity of the ligand, coordination number, the presence of phosphine, and K⋯F/O interactions on their O2 reactivity. K⋯F/O interactions were required to activate O2 in the monodentate-ligand-only family, whereas these connections did not affect O2 activation in the bidentate complexes, potentially due to the presence of phosphine. Both families formed trisanionic, trinuclear cores of the form {Cu33-O)2}3−. Intramolecular and intermolecular substrate oxidation were also explored and found to be influenced by the fluorinated ligand. Namely, {Cu33-O)2}3− from K[Cu(OR)2] could perform both monooxygenase reactivity and oxidase catalysis, whereas those from K[(R3P)Cu(pinF)] could only perform oxidase catalysis.

Graphical abstract: Cu(i)–O2 oxidation reactions in a fluorinated all-O-donor ligand environment

Article information

Article type
Perspective
Submitted
20 déc. 2018
Accepted
07 mars 2019
First published
14 mars 2019

Dalton Trans., 2019,48, 4759-4768

Author version available

Cu(I)–O2 oxidation reactions in a fluorinated all-O-donor ligand environment

S. E. N. Brazeau and L. H. Doerrer, Dalton Trans., 2019, 48, 4759 DOI: 10.1039/C8DT05028G

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements