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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