Electrochemical Behavior of Phosphine-Substituted Ruthenium(II) Polypyridine Complexes with a Single Labile Ligand
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A series of phosphine-substituted ruthenium polypyridine complexes, cis(P,Cl)-[Ru(trpy)(Pqn)Cl]PF6 (cis-Cl), trans(P,MeCN)-[Ru(trpy)(Pqn)(MeCN)](PF6)2 (trans-PN), cis(P,MeCN)-[Ru(trpy)(Pqn)(MeCN)](PF6)2 (cis-PN), and [Ru(trpy)(dppbz)(MeCN)](PF6)2 (PP), were synthesized and crystallographically characterized (trpy = 2,2′:6′,2″-terpyridine, Pqn = 8-(diphenylphosphanyl)quinoline, and dppbz = 1,2-bis(diphenylphosphanyl)benzene). In electrochemical measurements for cis-PN and PP, the reduction of cis-PN resulted in the formation of trans-PN via cis–trans isomerization and that of PP proceeded via a two-electron-transfer reaction. The mechanism of the electrochemical behaviors is discussed through consideration of five-coordinated species, [Ru(trpy)(Pqn)]n+ or [Ru(trpy)(dppbz)]n+ (n = 0–2), formed by liberation of a monodentate labile ligand.
