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The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Structural study on highly oxidized states of a water oxidation complex [RuIII(bpy)2(H2O)]2(mu-O)4+ by ruthenium
Kaoru Okamoto1, Jun Miyawaki, Kensuke Nagai
1Department of Chemistry, School of Science, The University of Tokyo, Tokyo 113-0033, Japan.
Abstract:
The oxidation-induced structural change of a water-oxidizing diruthenium complex, [(bpy)(2)(H(2)O)Ru(III)(micro-O)Ru(III)(OH(2))(bpy)(2)](4+) (bpy = 2,2'-bipyridine), was investigated by means of X-ray absorption spectroscopy. Ru K-edge XANES (X-ray absorption near-edge structure) spectra from the acidic solution and solid precipitates obtained by oxidation showed that the absorption edge shifts toward higher energy with a preedge feature slightly more enhanced than those of the lower oxidation states. This indicates that the higher oxidation state has a lower symmetry due to shortening of the Ru-O bonds that originated from the water ligands. The EXAFS (extended X-ray absorption fine structure) spectra were similar to those of the lower oxidation states, whose analysis revealed the existence of short Ru-O double bonds and an almost linear Ru-O-Ru angle (169 +/- 2 degrees ). Ab initio EXAFS simulations for several possible structural models suggest that the dimeric structure is maintained during the water oxidation reaction.
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