A ruthenium complex [ruthenium bis(2,2'-bipyridine)(2-mercaptopyridine)(pyridine)](PF6)2 was crystallographically characterized from its deprotonated form and was electrochemically investigated. In the deprotonated complex, the 2-mercaptopyridine ligand coordinates to the Ru atom only by the S atom; therefore, the N atom of the 2-mercaptopyridine ligand can be protonated. In a CH3CN solution, the complex shows a reversible redox couple attributed to RuIII/II-S. The addition of a base to the CH3CN solution of the complex gives irreversible voltammograms, implying electrochemically induced linkage isomerization between RuII-S and RuIII-N. Analysis of the observed cyclic voltammograms gave the equilibrium and rate constants for linkage isomerization: KIINS = 1.2 x 1018, KIIINS = 0.64, kIINS = 5 x 10 s(-1), kIISN = 4 x 10-17 s(-1), kIIINS = 0.26 s(-1), and kIIISN = 0.40 s(-1).
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