Experimental and quantum chemical characterization of the water oxidation cycle catalysed by [RuII(damp)(bpy)(H2O)]2+†
Abstract
The water-oxidation catalytic activity of [RuII(damp)(bpy)(H2O)]2+ has been determined from manometric and mass spectroscopy studies. Mechanistic details of the catalytic cycle have been studied both experimentally and using DFT and CASSCF/CASPT2 calculations. Characterisation of this Ru(II) complex and more highly oxidized catalytic intermediates has been accomplished through UV-vis and XAS spectroscopy, as well as through electrochemical techniques. Comparison of XAS spectra with CASSCF/CASPT2 calculations provides insight into the electronic structures of the more highly oxidized species, especially the degree to which oxidation occurs over both atoms of the Ru–O fragment. 18O-labelling experiments indicate that the O–O bond formation step proceeds via a water nucleophilic attack mechanism, and a detailed DFT analysis of the catalytic cycle predicts that step to be rate-determining and to take place for a formal Ru(V)![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
O species. A number of alternative higher energy pathways have also been characterised in order to provide a more complete vision of the whole system.
![Graphical abstract: Experimental and quantum chemical characterization of the water oxidation cycle catalysed by [RuII(damp)(bpy)(H2O)]2+](/en/Image/Get?imageInfo.ImageType=GA&imageInfo.ImageIdentifier.ManuscriptID=C2SC20399E&imageInfo.ImageIdentifier.Year=2012)
- This article is part of the themed collection: Physical Chemistry
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