含桥连Se—Se基团和两个(S_2C_2B_(10)H_(10))^(2-)离子的不饱和双核钌化合物与l-乙炔基环己醇的反应性(英文)

Reactivity of Dinuclear Ruthenium Complex Containing One μ-Se_2 Unit and Two 1,2-Dicarba-closo-dodecaborane-1,2-dithiolate Ligands toward (cyclo-C_6H_(10))(OH)C≡CH

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.

Treatment of （p-cymene）Ru2（μ-Se2）（S2C2B10H10）2 （1） with （cyclo-C6H10）（OH）C≡CH in dichloromethane led to addition complexes, （p-cymene）Ru2（μ-Se2）（S2C2B10H10）2（R1C=CR2） [R1=H, R2=（cyclo-C6H10）（OH） （2）; R1=（cyclo-C6H10）（OH）, R2=H （3）]. In boiling chloroform both 2 and 3 spontaneously lose water to generate two geometrical isomers （p-cymene）Ru2（μ-Se2）（S2C2B10H10）2 （R1C=CR2） [R1=H, R2=cyclo-C6H9 （4）; R1=cyclo-C6H9, R2=H （5）], respectively. Complexes 4 and 5 could be interconverted in refluxing toluene. In all products alkyne addition occurs at the sulfur atoms of the two individual chelating 1,2-dicarba-closo-dodecaborane-1,2-dithiolate ligands that leads to a change of the 16e Ru（IV） center in 1 to the 18e Ru（II） center in 2～5. The molecular structure of complex 2 has been determined by X-ray crystallography. All these complexes were characterized by elemental analysis, mass and NMR spectroscopy.