Syntheses, structures, and physicochemical properties of diruthenium compounds of tetrachlorocatecholate with metal-metal bonded Ru(3+)(mu-OR)(2)Ru(3+) and Ru(3.5+)(mu-OR)(2)Ru(3.5+) cores (R = CH(3) and C(2)H(5)).

Abstract

Metal-metal bonded Ru(3+)(mu-OR)(2)Ru(3+) and Ru(3.5+)(mu-OR)(2)Ru(3.5+) (R = CH(3) and CH(3)CH(2)) compounds with tetrachlorocatecholate (Cl(4)Cat) have been synthesized in the corresponding alcohol, MeOH and EtOH, from a nonbridged Ru(2+)-Ru(3+) compound, Na(3)[Ru(2)(Cl(4)Cat)(4)(THF)].3H(2)O.7THF (1). In alcohol solvents, compound 1 is continuously oxidized by oxygen to form Ru(3+)(mu-OR)(2)Ru(3+) and Ru(3.5+)(mu-OR)(2)Ru(3.5+) species. The presence of a characteristic countercation leads to selective isolation of either Ru(3+)(mu-OR)(2)Ru(3+) or Ru(3.5+)(mu-OR)(2)Ru(3.5+) as a stable adduct species. In methanol, Ph(4)PCl and dibenzo-18-crown-6-ether afford Ru(3+)(mu-OMe)(2)Ru(3+) species, [A](2)[Ru(2)(Cl(4)Cat)(4)(mu-OMe)(2)Na(2)(MeOH)(6)] ([A](+) = Ph(4)P(+) (2), [Na(dibenzo-18-crown-6)(H(2)O)(MeOH)](+) (3)), while benzo-15-crown-5-ether provides a Ru(3.5+)(mu-OMe)(2)Ru(3.5+) species, [Na(benzo-15-crown-5)(2)][Ru(2)(Cl(4)Cat)(4)(mu-OMe)(2)Na(2)(MeOH)(6)] (4). The air oxidation of 1 in a MeOH/EtOH mixed solvent (1:1 v/v) containing benzo-15-crown-5-ether provides a Ru(3.5+)(mu-OMe)(2)Ru(3.5+) species, [Na(benzo-15-crown-5)(H(2)O)][Ru(2)(Cl(4)Cat)(2)(mu-OMe)(2)Na(2)(EtOH)(2)(H(2)O)(2)(MeOH)(2)].(benzo-15-crown-5) (5). Similarly, the oxidation of 1 in ethanol with Ph(4)PCl provides a Ru(3.5+)(mu-OEt)(2)Ru(3.5+) species, (Ph(4)P)[Ru(2)(Cl(4)Cat)(4)(mu-OEt)(2)Na(2)(EtOH)(6)] (7). A selective formation of a Ru(3+)(mu-OEt)(2)Ru(3+) species, (Ph(4)P)(2)[Ru(2)(Cl(4)Cat)(4)(mu-OEt)(2)Na(2)(EtOH)(2)(H(2)O)(2)] (6), is found in the presence of pyrazine or 2,5-dimethylpyrazine. The crystal structures of these compounds, except 2 and 7, have been determined by X-ray crystallography, and all compounds have been characterized by several spectroscopic and magnetic investigations. The longer Ru-Ru bonds are found in the Ru(3+)(mu-OR)(2)Ru(3+) species (2.606(1) and 2.628(2) A for 3 and 6, respectively) compared with those of Ru(3.5+)(mu-OMe)(2)Ru(3.5+) species (2.5260(6) A and 2.514(2) A for 4 and 5, respectively). These structural features and magnetic and ESR data revealed the electronic configurations of sigma(2)pi(2)delta(2)delta(2)pi(2) and sigma(2)pi(2)delta(2)delta(2)pi(1) for Ru(3+)(mu-OR)(2)Ru(3+) and Ru(3.5+)(mu-OR)(2)Ru(3.5+), respectively, in which the former is diamagnetic and the latter is paramagnetic with S = (1)/(2) ground state. Compound 5 forms a one-dimensional chain with alternating arrangement of a Ru(3.5+)(mu-OMe)(2)Ru(3.5+) unit and a free benzo-15-crown-5-ether molecule by intermolecular hydrogen bonds (O(H(2)O).O(crown-ether) = 2.91-3.04 A). The cyclic voltammetry in DMF affords characteristic metal-origin voltammograms; two reversible and two quasi-reversible redox waves were observed. The feature of cyclic voltammograms for the Ru(3+)(mu-OR)(2)Ru(3+) species (2, 3, and 6) and the Ru(3.5+)(mu-OR)(2)Ru(3.5+) species (4 and 7) are similar to each other, indicating that both species are electrochemically stable. The isolation of the pyrazine-trans-coordinated species, [Ph(4)P][Ru(Cl(4)Cat)(2)(L)(2)] (L = pyrazine (8), 2,5-dimethylpyrazine (9)), revealed the selective isolation of 6 from pyrazine-containing solution. UV-vis spectral variation by ethanolysis for 9 demonstrated the selective conversion from the pyrazine-trans-coordinated species to the Ru(3+)(mu-OEt)(2)Ru(3+) species without an oxidation to the Ru(3.5+)(mu-OEt)(2)Ru(3.5+) species. This result suggests the presence of equilibrium between [Ru(Cl(4)Cat)(2)(L)(2)](-) and Ru(3+)(mu-OEt)(2)Ru(3+) species in the synthetic condition for 6.