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在二氯甲烷中,化合物(p-cymene)Ru2(μ-Se2)(S2C2B10H10)2(1)与l-乙炔基环己醇反应得到加成产物(p-cymene)-Ru2(μ-Se2)(S2C2B10H10)2(R1C=CR2)[R1=H,R2=(cyclo-C6H10)(OH)(2);R1=(cyclo-C6H10)(OH),R2=H(3)].化合物2和3在氯仿中加热回流可脱水分别生成4和5,二者在甲苯中进一步加热回流可实现相互转化.所有化合物中,炔烃碳碳三键选择性地加成在两个不同的(S2C2B10H10)2-配体的硫原子[S(2)和S(3)]上,从而使混合价双钌中心RuII/RuIV(18e/16e)转变为单一价态的RuII/RuII(18e/18e),得到进一步稳定的配合物.所有化合物通过元素分析、质谱、核磁共振进行了表征,并解析了化合物2的X衍射单晶结构.
The reaction of p-cymene Ru2 (μ-Se2) (S2C2B10H10) 2 (1) with 1-ethynylcyclohexanol in dichloromethane gives the product p- cymene-Ru2 (μ- Se2) R1 = (cyclo-C6H10) (OH) (2); R1 = (cyclo-C6H10) (OH), R2 = H (3)]. Compounds 2 and 3 can be dehydrated in chloroform to form 4 and 5, respectively, and the two can be converted into each other by further heating under reflux in toluene.In all compounds, the carbon-carbon triple bond of alkyne is selectively added to two different (S2C2B10H10) RuII / RuIV (18e / 16e) of the valence ruthenium centers into RuII / RuII (18e / 18e) of a single valence state on the sulfur atoms [S (2) and S (3) All the compounds were characterized by elemental analysis, mass spectrometry and nuclear magnetic resonance, and the structure of X-ray diffraction of compound 2 was analyzed.