Preparation, structure, and properties of the bis(μ-acetato)(μ-oxo)ruthenium(III) dimers [Ru2(μ-CH3COO)2(μ-O)(py) 6]2+ and [Ru2(μ-CH3COO)2(μ-O)(bpy) 2(py)2]2+

Yoichi Sasaki, Masakazu Suzuki, Tadashi Yamaguchi, Ayako Tokiwa, Masahiro Ebihara, Tadashi Yamaguchi, Chizuko Kabuto, Takashi Ochi, Tasuku Ito

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Abstract

Two ruthenium(III) dimers with a core structure similar to the methemerythrin active center have been prepared: [Ru2(μ-CH3COO)2(μ-O)(py) 6]2+ (1) and [Ru2(μ-CH3COO)2(μ-O)(bpy) 2(py)2]2+ (2) (py = pyridine, bpy = 2,2′-bipyridine). [Ru2-(CH3COO)2(O)(py)6](PF 6)2 crystallizes in the monoclinic space group C2/c with a = 42.229 (6) Å, b = 10.726 (1) Å, c = 20.470 (3) Å, β = 112.45 (1)°, V = 8568 (2) Å3, and Z = 8. The Ru-Ru distance is 3.251 (2) Å, and the direct metal-metal bond is absent. 1H NMR spectra of 1 in organic solvents are consistent with the solid-state structure. Those of 2 indicate that chelating bpy occupies the positions trans to the two acetate bridges. The complexes exhibit strong visible absorption bands at 581 nm (ε = 10 000 M-1 cm-1) and 599 nm (ε = 19 200) in CH3CN for 1 and 2, respectively. Cyclic voltammograms of both complexes in CH3CN show one reversible oxidation process and one irreversible reduction process in the range from -1 to +1 V vs Ag/AgClO4. The substitution reaction of py-d5 for the coordinated py in 1 shows that the position trans to the oxide bridge is at least 10 times more labile than the cis positions. The first-order rate constants in the presence of excess py-d5 (0.125 mol dm-3) are 2.2 × 10-4 and 5.5 × 10-5 s-1 for 1 and 2, respectively, at 50°C in CD3CN.

Original languageEnglish
Pages (from-to)4903-4908
Number of pages6
JournalInorganic Chemistry
Volume30
Issue number26
Publication statusPublished - 1991
Externally publishedYes

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Ruthenium
Dimers
ruthenium
Metals
dimers
preparation
Chelation
Organic solvents
Oxides
Absorption spectra
Rate constants
Acetates
Substitution reactions
Nuclear magnetic resonance
Oxidation
metals
acetates
pyridines
substitutes
solid state

ASJC Scopus subject areas

  • Inorganic Chemistry

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Preparation, structure, and properties of the bis(μ-acetato)(μ-oxo)ruthenium(III) dimers [Ru2(μ-CH3COO)2(μ-O)(py) 6]2+ and [Ru2(μ-CH3COO)2(μ-O)(bpy) 2(py)2]2+ . / Sasaki, Yoichi; Suzuki, Masakazu; Yamaguchi, Tadashi; Tokiwa, Ayako; Ebihara, Masahiro; Yamaguchi, Tadashi; Kabuto, Chizuko; Ochi, Takashi; Ito, Tasuku.

In: Inorganic Chemistry, Vol. 30, No. 26, 1991, p. 4903-4908.

Research output: Contribution to journalArticle

Sasaki, Yoichi ; Suzuki, Masakazu ; Yamaguchi, Tadashi ; Tokiwa, Ayako ; Ebihara, Masahiro ; Yamaguchi, Tadashi ; Kabuto, Chizuko ; Ochi, Takashi ; Ito, Tasuku. / Preparation, structure, and properties of the bis(μ-acetato)(μ-oxo)ruthenium(III) dimers [Ru2(μ-CH3COO)2(μ-O)(py) 6]2+ and [Ru2(μ-CH3COO)2(μ-O)(bpy) 2(py)2]2+ In: Inorganic Chemistry. 1991 ; Vol. 30, No. 26. pp. 4903-4908.
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abstract = "Two ruthenium(III) dimers with a core structure similar to the methemerythrin active center have been prepared: [Ru2(μ-CH3COO)2(μ-O)(py) 6]2+ (1) and [Ru2(μ-CH3COO)2(μ-O)(bpy) 2(py)2]2+ (2) (py = pyridine, bpy = 2,2′-bipyridine). [Ru2-(CH3COO)2(O)(py)6](PF 6)2 crystallizes in the monoclinic space group C2/c with a = 42.229 (6) {\AA}, b = 10.726 (1) {\AA}, c = 20.470 (3) {\AA}, β = 112.45 (1)°, V = 8568 (2) {\AA}3, and Z = 8. The Ru-Ru distance is 3.251 (2) {\AA}, and the direct metal-metal bond is absent. 1H NMR spectra of 1 in organic solvents are consistent with the solid-state structure. Those of 2 indicate that chelating bpy occupies the positions trans to the two acetate bridges. The complexes exhibit strong visible absorption bands at 581 nm (ε = 10 000 M-1 cm-1) and 599 nm (ε = 19 200) in CH3CN for 1 and 2, respectively. Cyclic voltammograms of both complexes in CH3CN show one reversible oxidation process and one irreversible reduction process in the range from -1 to +1 V vs Ag/AgClO4. The substitution reaction of py-d5 for the coordinated py in 1 shows that the position trans to the oxide bridge is at least 10 times more labile than the cis positions. The first-order rate constants in the presence of excess py-d5 (0.125 mol dm-3) are 2.2 × 10-4 and 5.5 × 10-5 s-1 for 1 and 2, respectively, at 50°C in CD3CN.",
author = "Yoichi Sasaki and Masakazu Suzuki and Tadashi Yamaguchi and Ayako Tokiwa and Masahiro Ebihara and Tadashi Yamaguchi and Chizuko Kabuto and Takashi Ochi and Tasuku Ito",
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T1 - Preparation, structure, and properties of the bis(μ-acetato)(μ-oxo)ruthenium(III) dimers [Ru2(μ-CH3COO)2(μ-O)(py) 6]2+ and [Ru2(μ-CH3COO)2(μ-O)(bpy) 2(py)2]2+

AU - Sasaki, Yoichi

AU - Suzuki, Masakazu

AU - Yamaguchi, Tadashi

AU - Tokiwa, Ayako

AU - Ebihara, Masahiro

AU - Yamaguchi, Tadashi

AU - Kabuto, Chizuko

AU - Ochi, Takashi

AU - Ito, Tasuku

PY - 1991

Y1 - 1991

N2 - Two ruthenium(III) dimers with a core structure similar to the methemerythrin active center have been prepared: [Ru2(μ-CH3COO)2(μ-O)(py) 6]2+ (1) and [Ru2(μ-CH3COO)2(μ-O)(bpy) 2(py)2]2+ (2) (py = pyridine, bpy = 2,2′-bipyridine). [Ru2-(CH3COO)2(O)(py)6](PF 6)2 crystallizes in the monoclinic space group C2/c with a = 42.229 (6) Å, b = 10.726 (1) Å, c = 20.470 (3) Å, β = 112.45 (1)°, V = 8568 (2) Å3, and Z = 8. The Ru-Ru distance is 3.251 (2) Å, and the direct metal-metal bond is absent. 1H NMR spectra of 1 in organic solvents are consistent with the solid-state structure. Those of 2 indicate that chelating bpy occupies the positions trans to the two acetate bridges. The complexes exhibit strong visible absorption bands at 581 nm (ε = 10 000 M-1 cm-1) and 599 nm (ε = 19 200) in CH3CN for 1 and 2, respectively. Cyclic voltammograms of both complexes in CH3CN show one reversible oxidation process and one irreversible reduction process in the range from -1 to +1 V vs Ag/AgClO4. The substitution reaction of py-d5 for the coordinated py in 1 shows that the position trans to the oxide bridge is at least 10 times more labile than the cis positions. The first-order rate constants in the presence of excess py-d5 (0.125 mol dm-3) are 2.2 × 10-4 and 5.5 × 10-5 s-1 for 1 and 2, respectively, at 50°C in CD3CN.

AB - Two ruthenium(III) dimers with a core structure similar to the methemerythrin active center have been prepared: [Ru2(μ-CH3COO)2(μ-O)(py) 6]2+ (1) and [Ru2(μ-CH3COO)2(μ-O)(bpy) 2(py)2]2+ (2) (py = pyridine, bpy = 2,2′-bipyridine). [Ru2-(CH3COO)2(O)(py)6](PF 6)2 crystallizes in the monoclinic space group C2/c with a = 42.229 (6) Å, b = 10.726 (1) Å, c = 20.470 (3) Å, β = 112.45 (1)°, V = 8568 (2) Å3, and Z = 8. The Ru-Ru distance is 3.251 (2) Å, and the direct metal-metal bond is absent. 1H NMR spectra of 1 in organic solvents are consistent with the solid-state structure. Those of 2 indicate that chelating bpy occupies the positions trans to the two acetate bridges. The complexes exhibit strong visible absorption bands at 581 nm (ε = 10 000 M-1 cm-1) and 599 nm (ε = 19 200) in CH3CN for 1 and 2, respectively. Cyclic voltammograms of both complexes in CH3CN show one reversible oxidation process and one irreversible reduction process in the range from -1 to +1 V vs Ag/AgClO4. The substitution reaction of py-d5 for the coordinated py in 1 shows that the position trans to the oxide bridge is at least 10 times more labile than the cis positions. The first-order rate constants in the presence of excess py-d5 (0.125 mol dm-3) are 2.2 × 10-4 and 5.5 × 10-5 s-1 for 1 and 2, respectively, at 50°C in CD3CN.

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