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

Article

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

Go Nakamura †‡, Masaya Okamura †‡, Masaki Yoshida ‡, Takayoshi Suzuki §, Hideo D. Takagi

† Department of Structural Molecular Science, School of Physical Sciences, The Graduate University for Advanced Studies (SOKENDAI), Shonan Village, Hayama-cho, Kanagawa 240-0193, Japan

‡ Institute for Molecular Science (IMS), 5-1 Higashiyama, Myodaiji, Okazaki, Aichi 444-8787,Japan

§ Graduate School of Natural Science and Technology,Okayama University, 3-1-1 Tsushima-naka, Kita-ku, Okayama 700-8530, Japan

Graduate School of Science and Research Center for Material Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya, Aichi 464-8602, Japan

Research Center of Integrative Molecular Systems (CIMoS), 38 Nishigo-naka, Myodaiji, Okazaki, Aichi 444-8585, Japan

# Japan Science and Technology Agency (JST), ACT-C, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012,Japan

Inorg. Chem., Article ASAP

DOI: 10.1021/ic5003644

Publication Date (Web): June 25, 2014

*E-mail for S.M.: masaoka@ims.ac.jp.

Synopsis

Three newly synthesized phosphine-substituted ruthenium polypyridine complexes exhibited distinct differences in their electrochemical behavior; reduction of cis-PN resulted in cis−trans isomerization to trans-PN, and that of PP proceeded via a two-electron-transfer reaction.

Section:

Inorganic Chemicals and Reactions

Abstract

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.

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