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- Title
Catalytic Water-Oxidation Activity of a Weakly Coupled Binuclear Ruthenium Polypyridyl Complex.
- Authors
Matias, Tiago A.; Mangoni, Ana P.; Toma, Sergio H.; Rein, Francisca N.; Rocha, Reginaldo C.; Toma, Henrique E.; Araki, Koiti
- Abstract
The catalytic oxidation of water by the binuclear complex [Ru2(H2O)2(bpy)2(tpy2ph)](PF6)4 [bpy = 2,2′-bipyridine; tpy2ph = 1,3-bis(4′-2,2′:6′,2′′-terpyridin-4-yl)benzene] was investigated comparatively to its mononuclear counterpart [Ru(H2O)(bpy)(phtpy)](PF6)2 (phtpy = 4′-phenyl-2,2′:6′,2′′-terpyridine). These catalysts were prepared from the synthesis of their precursor chloride complexes, which were also extensively characterized in this work. The H2O-RuII complexes were found to undergo proton-coupled electron-transfer processes to generate the redox species HO-RuIII, O=RuIV, and O=RuV. The catalytically active species, [RuV2(O)2(bpy)2(tpy2ph)]6+ and [RuV(O)(bpy)(phtpy)]3+, were generated electrochemically and by using cerium(IV) ammonium nitrate. In the presence of CeIV, the catalytic rates for O2 production by the binuclear and mononuclear species were 1.9 × 10-3 and 9.5 × 10-5 s-1, respectively. This superior catalytic performance of the binuclear complex suggests that, despite weak electronic coupling between the Ru centers, the second site could play an important mechanistic role in the formation of the activated species [(bpy)(OO)RuIV(tpy2ph)RuIII(OH)(bpy)]4+.
- Subjects
RUTHENIUM compound synthesis; OXIDATION of water; POLYPYRIDINES; CATALYSTS; CHEMICAL precursors; CHARGE exchange; ELECTROCATALYSIS; WATER electrolysis
- Publication
European Journal of Inorganic Chemistry, 2016, Vol 2016, Issue 36, p5547
- ISSN
1434-1948
- Publication type
Article
- DOI
10.1002/ejic.201600889