Preparation and study of a family of dinuclear Ru(II) complexes that catalyze the decomposition of water

An approach is developed for the four-electron oxidation of water to provide dioxygen that involves the juxtaposition of two Ru(II) centers such that a metal-bound water molecule might interact with one or both of the metals. The key element in this approach is an appropriate bridging ligand that will hold the metal assembly intact through the full redox cycle. Various synthetic approaches. to such ligands are described with the ultimate preparation of four closely related bis-tridentate polypyridine-type systems in which the bridging and distal portions of the ligand are varied. All of these ligands self-assemble with two Ru(II) centers bridged by a Cl ion in the equatorial plane and four axial monodentate substituted pyridines or N-methylimidazoles to form the well-organized catalyst complexes. These complexes are characterized by their distinctive H-1 NMR spectra as well as an X-ray structure of one representative species. The photophysical and electrochemical features of these complexes are consistent with electronegativity and delocalization effects in the equatorial and axial ligands. Of the 14 complexes studied, all but 2, which each contain four axial N-methylimidazole ligands, catalyze the decomposition of water in the presence of excess Ce(IV) as a sacrificial oxidant at pH = 1. Both the rates of oxygen evolution and the catalyst turnover numbers (TNs) are measured. For the active catalysts, the relative rates vary from 1 to 51. and the TNs measure from 80 to 689. Various analytical methods for making these measurements are discussed, and it is found that there is an approximately linear relationship between the rate and TN. Future work will involve optimization of these systems and studies aimed at a better understanding of the mechanism.