title: Structure and electronic configurations of the intermediates of water oxidation in blue ruthenium dimer catalysis.
abstract: Catalytic O(2) evolution with cis,cis-[(bpy)(2)(H(2)O)Ru(III)ORu(III)(OH(2))(bpy)(2)](4+) (bpy is 2,2-bipyridine), the so-called blue dimer, the first designed water oxidation catalyst, was monitored by UV-vis, EPR, and X-ray absorption spectroscopy (XAS) with ms time resolution. Two processes were identified, one of which occurs on a time scale of 100 ms to a few seconds and results in oxidation of the catalyst with the formation of an intermediate, here termed [3,4]'. A slower process occurring on the time scale of minutes results in the decay of this intermediate and O(2) evolution. Spectroscopic data suggest that within the fast process there is a short-lived transient intermediate, which is a precursor of [3,4]'. When excess oxidant was used, a highly oxidized form of the blue dimer [4,5] was spectroscopically resolved within the time frame of the fast process. Its structure and electronic state were confirmed by EPR and XAS. As reported earlier, the [3,4]' intermediate likely results from reaction of [4,5] with water. While it is generated under strongly oxidizing conditions, it does not display oxidation of the Ru centers past [3,4] according to EPR and XAS. EXAFS analysis demonstrates a considerably modified ligand environment in [3,4]'. Raman measurements confirmed the presence of the O-O fragment by detecting a new vibration band in [3,4]' that undergoes a 46 cm(-1) shift to lower energy upon (16)O/(18)O exchange. Under the conditions of the experiment at pH 1, the [3,4]' intermediate is the catalytic steady state form of the blue dimer catalyst, suggesting that its oxidation is the rate-limiting step.
authors.affiliation: Department of Physics, Purdue University, 525 Northwestern Avenue West Lafayette, Indiana 47907, United States.
authors.forename: Dooshaye
authors.initials: D
authors.lastname: Moonshiram
authors.forename: Jonah W
authors.initials: JW
authors.lastname: Jurss
authors.forename: Javier J
authors.initials: JJ
authors.lastname: Concepcion
authors.forename: Taisiya
authors.initials: T
authors.lastname: Zakharova
authors.forename: Igor
authors.initials: I
authors.lastname: Alperovich
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Meyer
authors.forename: Yulia
authors.initials: Y
authors.lastname: Pushkar