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[1]尹传奇,成军,张平,等.联吡啶钌配合物对末端炔烃的催化[J].武汉工程大学学报,2013,(06):1-6.[doi:103969/jissn16742869201306001]
 YIN Chuan qi,CHENG Jun,ZHANG Ping,et al.Cyclotrimerization of terminal Alkynes catalyzed by a Ruthenium (Ⅲ) complex bearing Bipyridine[J].Journal of Wuhan Institute of Technology,2013,(06):1-6.[doi:103969/jissn16742869201306001]
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联吡啶钌配合物对末端炔烃的催化(/HTML)
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《武汉工程大学学报》[ISSN:1674-2869/CN:42-1779/TQ]

卷:
期数:
2013年06期
页码:
1-6
栏目:
化学与化学工程
出版日期:
2013-06-30

文章信息/Info

Title:
Cyclotrimerization of terminal Alkynes catalyzed by a Ruthenium (Ⅲ) complex bearing Bipyridine
文章编号:
16742869(2013)06000106
作者:
尹传奇成军张平陈阔
武汉工程大学化工与制药学院,绿色化工过程教育部重点实验室,湖北省新型反应器与绿色化学工艺重点实验室,湖北 武汉 430074
Author(s):
YIN Chuanqi CHENG Jun ZHANG Ping CHEN Kuo
School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Key Laboratory for Green Chemical Processof Ministry of Education, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, Wuhan 430074, China
关键词:
联吡啶钌(Ⅲ)配合物取代苯催化环三聚机理
Keywords:
bipyridine Ru(III) complex substituted benzenes catalyzed cyclotrimerization mechanism
分类号:
O344.1; TQ032.41
DOI:
103969/jissn16742869201306001
文献标志码:
A
摘要:
以6,6’二甲基2,2’联吡啶为配体合成了二水合氯化顺二氯·二(6,6’二甲基2,2’联吡啶)合钌(Ⅲ)配合物,进一步用三氟甲基磺酸银脱氯得到三(三氟甲基)磺酸顺二水·二(6,6’二甲基2,2’联吡啶)合钌(Ⅲ)配合物.研究了后者对1己炔、苯乙炔和丙炔酸乙酯环三聚反应的催化作用. 实验结果显示环三聚产物具有区域选择性: 产物只有1,2,4三取代苯与1,3,5三取代苯两种同分异构体,且主要为1,2,4三取代苯. 催化机理研究表明, 三(三氟甲基)磺酸顺二水·二(6,6’二甲基2,2’联吡啶)合钌(Ⅲ)中的两个水分子配体首先被两分子炔烃取代生成π炔基配合物, 然后通过氧化偶联反应得到钌杂环戊二烯配合物;第三个炔烃分子经由插入反应或双烯加成反应生成钌杂环庚三烯或7钌杂双环\[2.2.1\]2,5庚二烯中间体, 随后发生还原消除反应得到三取代苯.
Abstract:
Cisbis(6,6’dimethyl2,2’bipyridine) dichloro ruthenium chloride dihydrate was synthesized by the reaction of ruthenium trichloride trihydrate with 6,6’dimethyl2,2’bipyridine. Cisbis(6,6’dimethyl2,2’bipyridine) diaqua ruthenium tri(trifluoromethyl sulfonate) was formed by dechloration of Cisbis(6,6’dimethyl2,2’bipyridine) dichloro ruthenium chloride in the presence of silver trifluoromethyl sulfonate. Cyclotrimerization of 1hexyne, phenylacetylene and Ethyl propiolate catalyzed by Cis bis(6,6’dimethyl2,2’bipyridine) diaqua ruthenium tri(trifluoromethyl sulfonate) was studied. The regioselectivity of the cyclotrimerization products is found: only 1,2,4 and 1,3,5 trisubstituted benzenes are formed, and the former is the major product. The catalytic mechanism reveals that the two water ligands in Cisbis(6,6’dimethyl2,2’bipyridine) diaqua ruthenium tri(trifluoromethyl sulfonate) are first replaced by two alkyne molecules to form πalkyne complex, which is then transformed to heteroruthenium cyclopentadiene complex by oxidized coupling reaction. Heteroruthenium cycloheptatriene or 7heteroruthenium bicyclo\[2.2.1\]2,5heptadiene is generated by the insertion reaction or DielsAlder reaction of the third alkyne molecule with the hetero ruthenium cyclopentadiene complex. The cyclotrimerization products are finally formed by reduced elimination reaction.

参考文献/References:

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备注/Memo

备注/Memo:
收稿日期:20130412基金项目:湖北省自然科学基金(2009CDB357);湖北省教育厅基金(D20111504);绿色化工过程教育部重点实验室基金(GCP200909)作者简介:尹传奇(1966), 男, 湖北鄂州人, 教授, 博士, 硕士研究生导师. 研究方向: 过渡金属配合物的催化反应.
更新日期/Last Update: 2013-07-11