Novel lantern-type dinuclear complexes in unusual electronic states with strong π-donor bridging ligands

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The reaction of [Ru_2(O_2CMe)_4Cl] with neat 4,5-dimethyl-2-methylaminothiazole (Hdmat) gave an aminothiazolato-bridged paddlewheel Ru_2^<5+> complex, [Ru_2(dmat)_4Cl](1). The corresponding Ru_2^<6+> species, [Ru_2(dmat)_4Cl]PF_6(2), was produced by electrochemical oxidation. Their magnetic susceptibility data of 1.7 and 2.89 BM for 1 and 2 are consistent with the electron configurations of σ^2π^4δ^2π^<*3> and σ^2π^4δ^2π^<*2> for 1 and 2, respectively. The Ru-Ru distances of 1 and 2 are 2.4317(9) and 2.3326(9)Å, respectively. The elongation of the M-M distance on the addition of one electron into a π^* orbital is similar to that observed in a paddlewheele dirhodium complex. The reaction of [Ru_2(O_2CMe)_4Cl] with neat 4-methyl-2-methylaminothiazole (Hmmat) gave [Ru_2(mmat)_4Cl](3) that is very similar to 1. However, the solubility of 3 to common organic solvents are poor. The reaction of 1 with LiCCPh afforded alkylidyne ligated complex [Ru_2(O_2CMe)_4(CCPh)](4). Its Ru-Ru distance is 2.4697(9) Å which is ca.0.03 Å longer than that of 1. Complex 4 is oxidized to Ru_2^<6+> at E_<1/2>=-0.39 V vs Fc^+/Fc which is ca.0.1 V more negative than that of 1.