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

doi:10.6023/A13030346

化学学报 ›› 2013, Vol. 71 ›› Issue (06): 892-896.DOI: 10.6023/A13030346 上一篇下一篇

研究论文

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

胡久荣^a,b, 彭化南^b, 胡昕^b, 叶红德^b, 燕红^a

a 南京大学化学化工学院配位化学国家重点实验室南京 210093;
b 上饶师范学院化学化工学院上饶 334001

投稿日期:2013-03-29 发布日期:2013-05-02
通讯作者: 胡久荣,hyan1965@nju.edu.cn;燕红,jiuronghu@163.com E-mail:hyan1965@nju.edu.cn;jiuronghu@163.com
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

Hu Jiurong^a,b, Peng Huanan^b, Hu Xin^b, Ye Hongde^b, Yan Hong^a

a State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Jiangsu 210093;
b School of Chemistry and Chemical Engineering, Shangrao Normal University, Jiangxi 334001

Received:2013-03-29 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).

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摘要/Abstract

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Ru^II/Ru^IV (18e/16e)转变为单一价态的Ru^II/Ru^II (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.

Key words: ortho-carborane, (cyclo-C₆H₁₀)(OH)C≡CH, chalcogenide element, ruthenium complexes, synthesis

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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.

Hu Jiurong, Peng Huanan, Hu Xin, Ye Hongde, Yan Hong. 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[J]. Acta Chimica Sinica, 2013, 71(06): 892-896.

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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

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

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