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

[Ru_2(O_2CMe)_4Cl]与整齐的4,5-二甲基-2-甲基氨基噻唑（Hdmat）反应得到了氨基噻唑桥接的桨轮状络合物[Ru_2(dmat)_4Cl](1)。电化学氧化法制备了相应的Ru_2^<6+>物质[Ru_2(dmat)_4Cl]PF_6(2)。1和2的磁化率分别为1.7和2.89 BM，与1和2的σ^2π^4δ^2π^<*3>和σ^2π^4δ^2π^<*2>的电子构型一致。1和2的Ru-Ru距离分别为2.4317(9)和2.3326(9)Å。在π^*轨道上加入一个电子时，M-M距离的延长与在桨轮式镝配合物中观察到的相似。[Ru_2(O_2CMe)_4Cl]与整齐的4-甲基-2-甲基氨基噻唑（Hmmat）反应得到[Ru_2(mmat)_4Cl](3)，与1非常相似。但3对普通有机溶剂的溶解度较差。1与LiCCPh反应得到烷基炔连接配合物[Ru_2(O_2CMe)_4(CCPh)](4)。其Ru-Ru距离为2.4697(9)Å，比1长约0.03 Å。配合物4在E_<1/2>=-0.39 V vs Fc^+/Fc下氧化为Ru_2^<6+>，比1负0.1 V。

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.