@article { ISI:000290457700058,
	title = {Unraveling the Roles of the Acid Medium, Experimental Probes, and Terminal Oxidant, (NH4)(2){[}Ce(NO3)(6)], in the Study of a Homogeneous Water Oxidation Catalyst},
	journal = {INORGANIC CHEMISTRY},
	volume = {50},
	number = {8},
	year = {2011},
	month = {APR 18},
	pages = {3662-3672},
	abstract = {The oxidation of water catalyzed by {[}Ru(tpy)(bpy)(OH2)](ClO4)(2) (1; tpy = 2,2{\textquoteright};6 {\textquoteleft}{\textquoteright},2 {\textquoteleft}{\textquoteright}-terpyridine; bpy = 2,2{\textquoteright}-bipyridine) is evaluated in different acidic media at variable oxidant concentrations. The observed rate of dioxygen evolution catalyzed by 1 is found to be highly dependent on pH and the identity of the acid; e.g., d{[}O-2]/dt is progressively faster in H2SO4, CF3SO3H (HOTf), HClO4, and HNO3, respectively. This trend does not track with thermodynamic driving force of the electron-transfer reactions between the terminal oxidant, (NH4)(2){[}Ce(NO3)(6)] (CAN), and Ru catalyst in each of the acids. The particularly high reactivity in HNO3 is attributed to the NO3- anion: (i) enabling relatively fast electron-transfer steps; (ii) participating in a base-assisted concerted atom-proton transfer process that circumvents the formation of high energy intermediates during the O-O bond formation process; and (iii) accelerating the liberation of dioxygen from the catalyst. Consequently, the position of the rate-determining step within the catalytic cycle can be affected by the acid medium. These factors collectively contribute to the position of the rate-determining step within the catalytic cycle being affected by the acid medium. This offering also outlines how other experimental issues (e.g., spontaneous decay of the Ce(IV) species in acidic media; CAN/catalyst molar ratio; types of catalytic probes) can affect the Ce(IV)-driven oxidation of water catalyzed by homogeneous molecular complexes.},
	issn = {0020-1669},
	doi = {10.1021/ic2000188},
	author = {Wasylenko, Derek J. and Ganesamoorthy, Chelladurai and Henderson, Matthew A. and Berlinguette, Curtis P.}
}
