TY - JOUR
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 - Kabuto, Chizuko
AU - Ochi, Takashi
AU - Ito, Tasuku
AU - Nagasawa, Akira
AU - Tokiwa, Ayako
AU - Ebihara, Masahiro
PY - 1991/12/1
Y1 - 1991/12/1
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- (CH,COO)2(O)(py)6](PF6)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 (e = 10000 M−1 cm−1) and 599 nm (є = 19200) 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-ds 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- (CH,COO)2(O)(py)6](PF6)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 (e = 10000 M−1 cm−1) and 599 nm (є = 19200) 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-ds 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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U2 - 10.1021/ic00026a011
DO - 10.1021/ic00026a011
M3 - Article
AN - SCOPUS:0000015933
SN - 0020-1669
VL - 30
SP - 4903
EP - 4908
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 26
ER -