| 宋雪,成军,张平,尹传奇.取代联吡啶钌配合物对末端炔烃的催化环三聚作用[J].分子催化,2014,(2):126-131 |
| 取代联吡啶钌配合物对末端炔烃的催化环三聚作用 |
| Cyclotrimerization of Terminal Alkynes Catalyzed by Ruthenium Complexes Containing Substituted Bipyridine Ligands |
| 投稿时间：2013-07-20 修订日期：2013-12-16 |
| DOI： |
| 中文关键词: 取代联吡啶 钌配合物 末端炔烃 催化环三聚 区域选择性 |
| 英文关键词:substituted bipyridine ligand ruthenium complex terminal alkyne catalyzed cyclotrimerization regioselectivity |
| 基金项目:湖北省自然科学基金(No. 2009CDB357)、绿色化工过程教育部重点实验室基金和湖北省教育厅基金(No. D20111504) |
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| 中文摘要: |
| RuCl3•2H2O分别与6,6’-二甲基-2,2’-联吡啶（dmbp）和2,2’-联吡啶-6,6’-二甲醛（bpda）反应生成[cis-Ru(L)2Cl2]Cl•2H2O (L=dmbp, bpda)，进一步用CF3SO3Ag脱氯得到[cis-Ru(L)2(H2O)2](CF3SO3)3．研究了四种配合物对1-己炔、苯乙炔和丙炔酸乙酯的催化环三聚作用，发现脱氯后的含水配合物催化活性有显著提高；体系中有水存在时，丙炔酸乙酯环三聚具有很强的区域选择性。催化机理研究表明, 该催化过程为催化[2+2+2]环加成反应．钌杂环庚三烯或7-钌杂双环[2.2.1]-2,5-庚二烯是关键中间体，联吡啶配体上的6-甲酰基取代基水合后通过与丙炔酸乙酯的羰基形成分子内氢键影响环三聚产物的区域选择性． |
| 英文摘要: |
| [Cis-Ru(dmbp)2Cl2]Cl•2H2O and [cis-Ru(bpda)2Cl2]Cl•2H2O were synthesized by the reaction of RuCl3•3H2O with 6,6’-dimethyl-2,2’-bipyridine (dmbp) and 2,2’-bipyridine-6,6'-dicarboxaldehyde (bpda), respectively. The catalytic activity of the four complexes on catalyzed cyclotrimerization of 1-hexyne, phenylacetylene and ethyl propiolate was investigated. The higher catalytic activity of two dechlorinated complexes and higher regioseletivity of cyclotrimerization of ethyl propiolate in the presence of water were found. The catalytic mechanism is postulated to be a Ru-catalyzed [2+2+2] cycloaddition reaction, Ru-heterocycloheptatrienes or 7-Ru heterobicyclo[2.2.1]-2,5-heptadienes are postulated to be the key intermediates. The regioseletivity of cyclotrimerization is affected by the intramolecular hydrogen bond between the hydrated formyl group in the 6-position of bipyridine ligand and the carbonyl in ethyl propiolate ligand. |
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