Issue 5, 2016

Molecular ruthenium water oxidation catalysts carrying non-innocent ligands: mechanistic insight through structure–activity relationships and quantum chemical calculations

Abstract

Robust catalysts that mediate H2O oxidation are of fundamental importance for the development of novel carbon-neutral energy technologies. Herein we report the synthesis of a group of single-site Ru complexes. Structure–activity studies revealed that the individual steps in the oxidation of H2O depended differently on the electronic properties of the introduced ligand substituents. The mechanistic details associated with these complexes were investigated experimentally along with quantum chemical calculations. It was found that O–O bond formation for the developed Ru complexes proceeds via high-valent RuVI species, where the capability of accessing this species is derived from the non-innocent ligand architecture. This cooperative catalytic involvement and the ability of accessing RuVI are intriguing and distinguish these Ru catalysts from a majority of previously reported complexes, and might generate unexplored reaction pathways for activation of small molecules such as H2O.

Graphical abstract: Molecular ruthenium water oxidation catalysts carrying non-innocent ligands: mechanistic insight through structure–activity relationships and quantum chemical calculations

Supplementary files

Article information

Article type
Paper
Submitted
06 Oct 2015
Accepted
26 Oct 2015
First published
30 Oct 2015

Catal. Sci. Technol., 2016,6, 1306-1319

Molecular ruthenium water oxidation catalysts carrying non-innocent ligands: mechanistic insight through structure–activity relationships and quantum chemical calculations

M. D. Kärkäs, R. Liao, T. M. Laine, T. Åkermark, S. Ghanem, P. E. M. Siegbahn and B. Åkermark, Catal. Sci. Technol., 2016, 6, 1306 DOI: 10.1039/C5CY01704A

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