Electrochemical and Resonance Raman Spectroscopic Studies of Water-Oxidizing Ruthenium Terpyridyl-Bipyridyl Complexes.

ABSTRACT

The irreversible conversion of single-site water-oxidation catalysts (WOC) into more rugged catalysts structurally related to [(trpy)(5,5'-X2 -bpy)RuIV (µ-O)RuIV (trpy)(O)(H2 O)]4+ (X=H, 1-dn4+ ; X=F, 2-dn4+ ; bpy=2,2'-bipyridine; trpy=2,2'6',2"-terpyridine) represents a critical issue in the development of active and durable WOCs. In this work, the electrochemical and acid-base properties of 1-dn4+ and 2-dn4+ were evaluated. In situ resonance Raman spectroscopy was employed to characterize the species formed upon the stoichiometric oxidation of the single-site catalysts and demonstrated the formation of high-oxidation-state mononuclear Ru=O and RuO-O complexes. Under turnover conditions, the dinuclear intermediates, 1-dn4+ and 2-dn4+ as well as the previously proposed [RuVI (trpy)(O)2 (H2 O)]2+ complex (32+ ) are formed. Complex 32+ is a pivotal intermediate that provides access to the formation of dinuclear species. Single-crystal X-ray diffraction analysis of the isolated complex [RuIV (O)(trpy)(5,5'-F2 -bpy)]2+ reveals a clear elongation of the Ru-N bond trans to the oxido ligand that documents the weakness of this bond, which promotes the release of the bpy ligand and the subsequent formation of 32+ .