Add time:08/11/2019         Source:sciencedirect.com

Ruthenium μ-oxo dimers with chloro-substituted 2,2′-bipyridines [L2(H2O)RuIIIORuIII(OH2)L2]4+ (L= 4,4′-dichloro- or 5,5′-dichloro-2,2′-bipyridine) were synthesized. Electrochemical studies on the complexes showed that the RuIII|O|RuIII dimer undergoes a reversible one-electron oxidation to RuIII|O|RuIV followed by a reversible multi-electron oxidation assignable as the oxidation of RuIII|O|RuIV to RuIV|O|RuV. The RuIII|O|RuIV and RuIV|O|RV species were characterized by thin-layer spectroelectrochemistry. The RuIV|O|RuV dimer is an active catalyst for the chemical or electrochemical oxidation of water to dioxygen. Upon reduction, the RuIII|O|RuIII dimer undergoes reductive cleavage to give [RuIIL2(H2O)2]2+. The chloro-substituted ruthenium dimers are more stable towards reductive cleavage in mildly acidic media than the unsubstituted [(bpy)2(H2O)RuIIIORuIII(OH2)(bpy)2]4+ (bpy= 2,2′-bipyridine).

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