Oxo-Centered Mixed-Ligand Triruthenium Complexes Having Redox-Active N-Methyl-4,4′-bipyridinium Ions (mbpy+). Reversible Multistep Electrochemical Properties of [Ru2IIIRuII(μ3-O)(μ-CH3CO 2)6(mbpy+)2(CO)]2+

Masaaki Abe*, Yoichi Sasaki, Yasuko Yamada, Keiichi Tsukahara, Shigenobu Yano, Tadashi Yamaguchi, Masato Tominaga, Isao Taniguchi, Tasuku Ito

*この研究の対応する著者

研究成果: Article査読

97 被引用数 (Scopus)

抄録

A new series of oxo-centered acetate-bridged triruthenium comlexes having two redox-active N-methyl-4,4′-bipyridinium ions (mbpy+) have been prepared, and their reversible multistep and multielectron electrochemical properties are reported: [Ru2IIIRuII3-O)(μ-CH 3CO2)6(mbpy+2(CO)] 2+ and [Ru3III3-O)(μ-CH3CO 2)6(mbpy+)2-(L)]3+ (L = H2O, pyrazine (pz), pyridine (py), imidazole (Him), and 4-(dimethylamino)pyridine (dmap)). Among these series, the CO complex, [Ru2IIIRuII3-O)(μ-CH 3CO2)6(mbpy+) 2(CO)](ClO4)2·2DMF (1b·2DMF) was structurally characterized by X-ray crystallography. 1b·2DMF crystallizes in the monoclinic space group P21/m (No. 11) with a = 8.740(6) Å, b = 32.269(6) Å, c = 10.276(4) Å, β = 103.37(5)°, V = 2820(2) Å3, Z = 2, dcalcd = 1.636 g cm-3, and R = 0.071 (Rw = 0.074) for 5277 independent reflections (|Fo| > 3σ(|Fo|). The (CO)-Ru⋯Ru distance (3.410(2) Å) is appreciably longer than the other Ru⋯Ru distance (3.276(2) Å), indicating that the trinuclear core is in the valence-trapped Ru2IIIRuII(CO) oxidation state. The cyclic voltammogram of [Ru2IIIRuII3-O)(μ-CH 3CO2)6(mbpy+) 2(CO)](PF6)2 (1a) shows a total of seven reversible one-electron redox steps at E1/2 = +0.90, +0.26, -1.07, -1.17, -1.56, -1.97, and -2.32 V and one irreversible step at Epc = -2.99 V vs Fc/Fc+ in a 0.1 M [(n-C4H9)4N]PF6-CH3CN solution (M = mol dm-3). All of the waves are clearly assignable to the triruthenium "Ru33-O)" core-based or mbpy+ ligand-based processes. The splitting of each ligand-based redox processes (mbpy+/mbpy' and mbpy/mbpy-) into two one-electron steps indicates that electronic interactions between two terminal ligands occur through the triruthenium cluster core. Other mixed-ligand Ru3III analogs also show multistep redox behavior involving a total of eight or nine electrons. While the extent of interactions between ligands is much smaller than that found in the CO complex, it is systematically changed by the nature of L; with more basic L, interactions between two mbpy+ ligands become larger.

本文言語English
ページ(範囲)6724-6734
ページ数11
ジャーナルInorganic Chemistry
35
23
出版ステータスPublished - 1996 12 1
外部発表はい

ASJC Scopus subject areas

  • 物理化学および理論化学
  • 無機化学

フィンガープリント

「Oxo-Centered Mixed-Ligand Triruthenium Complexes Having Redox-Active N-Methyl-4,4′-bipyridinium Ions (mbpy<sup>+</sup>). Reversible Multistep Electrochemical Properties of [Ru<sub>2</sub><sup>III</sup>Ru<sup>II</sup>(μ3-O)(μ-CH<sub>3</sub>CO <sub>2</sub>)<sub>6</sub>(mbpy<sup>+</sup>)<sub>2</sub>(CO)]<sup>2+</sup>」の研究トピックを掘り下げます。これらがまとまってユニークなフィンガープリントを構成します。

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