含桥连Se-Se基团和两个(S2C2B10H10)2-离子的不饱和双核钌化合物与1-乙炔基环己醇的反应性

摘要

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.%在二氯甲烷中,化合物(p-cymene)Ru2(μ-Se2)(S2C2B10H10)2 (1)与1-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.