Oxo-Centered Mixed-Ligand Triruthenium Complexes Having Redox-Active N-Methyl-4,4′-bipyridinium Ions (mbpy+). Reversible Multistep Electrochemical Properties of [Ru2 IIIRuII(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

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Abstract

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: [Ru2 IIIRuII3-O)(μ-CH 3CO2)6(mbpy+ 2(CO)] 2+ and [Ru3 III3-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, [Ru2 IIIRuII3-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 Ru2 IIIRuII(CO) oxidation state. The cyclic voltammogram of [Ru2 IIIRuII3-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 Ru3 III 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.

Original languageEnglish
Pages (from-to)6724-6734
Number of pages11
JournalInorganic Chemistry
Volume35
Issue number23
Publication statusPublished - 1996
Externally publishedYes

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Carbon Monoxide
Electrochemical properties
Ions
Ligands
ligands
ions
methylidyne
pyridines
Electrons
electrons
Pyrazines
pyrazines
interactions
imidazoles
X ray crystallography
crystallography
Oxidation-Reduction
acetates
analogs
Acetates

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Oxo-Centered Mixed-Ligand Triruthenium Complexes Having Redox-Active N-Methyl-4,4′-bipyridinium Ions (mbpy+). Reversible Multistep Electrochemical Properties of [Ru2 IIIRuII(μ3-O)(μ-CH3CO 2)6(mbpy+)2(CO)]2+ . / Abe, Masaaki; Sasaki, Yoichi; Yamada, Yasuko; Tsukahara, Keiichi; Yano, Shigenobu; Yamaguchi, Tadashi; Tominaga, Masato; Taniguchi, Isao; Ito, Tasuku.

In: Inorganic Chemistry, Vol. 35, No. 23, 1996, p. 6724-6734.

Research output: Contribution to journalArticle

Abe, Masaaki ; Sasaki, Yoichi ; Yamada, Yasuko ; Tsukahara, Keiichi ; Yano, Shigenobu ; Yamaguchi, Tadashi ; Tominaga, Masato ; Taniguchi, Isao ; Ito, Tasuku. / Oxo-Centered Mixed-Ligand Triruthenium Complexes Having Redox-Active N-Methyl-4,4′-bipyridinium Ions (mbpy+). Reversible Multistep Electrochemical Properties of [Ru2 IIIRuII(μ3-O)(μ-CH3CO 2)6(mbpy+)2(CO)]2+ In: Inorganic Chemistry. 1996 ; Vol. 35, No. 23. pp. 6724-6734.
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title = "Oxo-Centered Mixed-Ligand Triruthenium Complexes Having Redox-Active N-Methyl-4,4′-bipyridinium Ions (mbpy+). Reversible Multistep Electrochemical Properties of [Ru2 IIIRuII(μ3-O)(μ-CH3CO 2)6(mbpy+)2(CO)]2+",
abstract = "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: [Ru2 IIIRuII(μ3-O)(μ-CH 3CO2)6(mbpy+ 2(CO)] 2+ and [Ru3 III(μ3-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, [Ru2 IIIRuII(μ3-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) {\AA}, b = 32.269(6) {\AA}, c = 10.276(4) {\AA}, β = 103.37(5)°, V = 2820(2) {\AA}3, 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) {\AA}) is appreciably longer than the other Ru⋯Ru distance (3.276(2) {\AA}), indicating that the trinuclear core is in the valence-trapped Ru2 IIIRuII(CO) oxidation state. The cyclic voltammogram of [Ru2 IIIRuII(μ3-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 {"}Ru3(μ3-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 Ru3 III 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.",
author = "Masaaki Abe and Yoichi Sasaki and Yasuko Yamada and Keiichi Tsukahara and Shigenobu Yano and Tadashi Yamaguchi and Masato Tominaga and Isao Taniguchi and Tasuku Ito",
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TY - JOUR

T1 - Oxo-Centered Mixed-Ligand Triruthenium Complexes Having Redox-Active N-Methyl-4,4′-bipyridinium Ions (mbpy+). Reversible Multistep Electrochemical Properties of [Ru2 IIIRuII(μ3-O)(μ-CH3CO 2)6(mbpy+)2(CO)]2+

AU - Abe, Masaaki

AU - Sasaki, Yoichi

AU - Yamada, Yasuko

AU - Tsukahara, Keiichi

AU - Yano, Shigenobu

AU - Yamaguchi, Tadashi

AU - Tominaga, Masato

AU - Taniguchi, Isao

AU - Ito, Tasuku

PY - 1996

Y1 - 1996

N2 - 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: [Ru2 IIIRuII(μ3-O)(μ-CH 3CO2)6(mbpy+ 2(CO)] 2+ and [Ru3 III(μ3-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, [Ru2 IIIRuII(μ3-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 Ru2 IIIRuII(CO) oxidation state. The cyclic voltammogram of [Ru2 IIIRuII(μ3-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 "Ru3(μ3-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 Ru3 III 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.

AB - 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: [Ru2 IIIRuII(μ3-O)(μ-CH 3CO2)6(mbpy+ 2(CO)] 2+ and [Ru3 III(μ3-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, [Ru2 IIIRuII(μ3-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 Ru2 IIIRuII(CO) oxidation state. The cyclic voltammogram of [Ru2 IIIRuII(μ3-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 "Ru3(μ3-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 Ru3 III 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.

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JF - Inorganic Chemistry

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