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

[Ru_2(O_2CMe)_4Cl]与4，5-二甲基-2-甲基氨基噻唑(Hdmat)反应，得到了一种氨基噻唑桥联的叶轮配合物[Ru_2(DMAT)_4Cl](1)。通过电化学氧化生成了相应的Ru_2^&lt；6&gt；物种[Ru_2(Dmat)_4CL]PF_6(2)。它们的磁化率数据分别为1.7BM和2.89BM，分别与1和2的σ^2π^4δ^2π^；*3&gt；和σ^2π^4δ^2π^；*2&gt；1和2的Ru-Ru距离分别为2.4317(9)和2.3326(9)Å。将一个电子加到π^*轨道上，M-M距离的延长与在浆轮分子中观察到的结果相似。[Ru_2(O_2CMe)_4Cl]与纯净的4-甲基-2-甲基氨基噻唑(HMMAT)反应生成与1非常相似的[Ru_2(MMat)_4Cl](3)，但3对常见有机溶剂的溶解性较差。1与LiCCPh反应生成亚烷基连接配合物[Ru_2(O_2CMe)_4(CCPh)](4)。其Ru-Ru距离为2.4697(9)Å，比1长约0.03Å。在E_1/2&gt；=-0.39V时，配合物4被氧化为Ru_2^&lt；6&gt；

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.