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l-乙炔基环己醇的反应性
收稿日期: 2013-03-29
网络出版日期: 2013-05-02
基金资助
项目受国家自然科学基金(Nos. 21261020, 21271102)、江西省高等学校科技落地计划(No. KJLD12094)和江西省普通高校重点实验室科研项目(No. GJJ12704)资助.
Reactivity of Dinuclear Ruthenium Complex Containing One μ-Se2 Unit and Two 1,2-Dicarba-closo-dodecaborane-1,2-dithiolate Ligands toward (cyclo-C6H10)(OH)C≡CH
Received date: 2013-03-29
Online published: 2013-05-02
Supported by
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), and the Science and Technology Research Project of Key Laboratory of Higher Institutions of Jiangxi Province (No. GJJ12704).
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.
胡久荣 , 彭化南 , 胡昕 , 叶红德 , 燕红 . 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l-乙炔基环己醇的反应性[J]. 化学学报, 2013 , 71(06) : 892 -896 . DOI: 10.6023/A13030346
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.
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