摘要
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.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2013年第6期892-896,共5页
Acta Chimica Sinica
基金
Project supported by the National Natural Science Foundation of China(Nos.21261020,21271102)
the Scientific and Technological Landing Project of Higher Education of Jiangxi Province(No.KJLD12094)
the Science and Technology Research Project of Key Laboratory of Higher Institutions of Ji -angxi Province(No.GJJ12704)~~
关键词
邻位-碳硼烷
1-乙炔基环己醇
硫族元素
钌配合物
合成
ortho-carborane
(cyclo-C6H10)(OH)C≡CH
chalcogenide element
ruthenium complexes
synthesis