Electrochemical Behavior of Phosphine-Substituted Ruthenium(II) Polypyridine Complexes with a Single Labile Ligand

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• 作者：Go Nakamura ; Masaya Okamura ; Masaki Yoshida ; Takayoshi Suzuki ; Hideo D. Takagi ; Mio Kondo ; Shigeyuki Masaoka
• 刊名：Inorganic Chemistry
• 出版年：2014
• 出版时间：July 21, 2014
• 年：2014
• 卷：53
• 期：14
• 页码：7214-7226
• 全文大小：613K
• ISSN：1520-510X

文摘

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鈥?6鈥?2鈥?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鈥?i>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鈥?), formed by liberation of a monodentate labile ligand.