| 单氢钌配合物催化氢化苯乙烯的位阻效应 |
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| 引用本文： | 尹传奇,冯权武,柏正武. 单氢钌配合物催化氢化苯乙烯的位阻效应[J]. 化学学报, 2009, 67(6): 519-522 |
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| 作者姓名： | 尹传奇 冯权武 柏正武 |
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| 作者单位： | 武汉工程大学绿色化工过程省部共建教育部重点实验室,武汉,430074;武汉工程大学绿色化工过程省部共建教育部重点实验室,武汉,430074;武汉工程大学绿色化工过程省部共建教育部重点实验室,武汉,430074 |
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| 基金项目： | 湖北省自然科学基金，湖北省教育厅资助项目 |
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| 摘 要： | 研究了溶剂分别为 THF, H2O/THF, CH3CN/THF以及ROH/THF (R＝Me, Et, iso-Pr, tert-Bu)条件下TpRuH(PPh3)- (CH3CN) [Tp＝hydrotris(pyrazolyl)borate]催化氢化苯乙烯生成乙基苯的反应, 发现向干燥THF体系中添加微量 H2O, CH3CN或ROH对催化反应都具有显著的促进作用. 催化机理研究表明, 小分子添加物首先取代TpRuH(PPh3)(CH3CN)中的PPh3配体形成中间体TpRuH(CH3CN)L (L＝H2O, CH3CN或ROH), 降低空间位阻, CH3CN配体随后被苯乙烯取代生成中间体 TpRuH(H2C＝CHPh)L; η2-苯乙烯插入Ru—H键后形成的Ru-烷基中间物与H2反应生成η2-H2配合物 TpRu(CH2CH2Ph)(H2)L或TpRu[CH(CH3)Ph](H2)L, 进而发生σ-复分解反应生成乙基苯完成催化循环.
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| 关 键 词： | 苯乙烯 位阻 催化氢化 单氢钌配合物 |
| 收稿时间： | 2008-09-28 |
| 修稿时间： | 2008-10-27 |
Steric Hindrance Effect on Hydrogenation of Styrene Catalyzed by Ruthenium Hydride Complex |
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| Yin,Chuanqi,Feng,Quanwu,Bai,Zhengwu. Steric Hindrance Effect on Hydrogenation of Styrene Catalyzed by Ruthenium Hydride Complex[J]. Acta Chimica Sinica, 2009, 67(6): 519-522 |
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| Authors: | Yin Chuanqi Feng Quanwu Bai Zhengwu |
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| Affiliation: | Key Laboratory for Green Chemical Process of Ministry of Education;Wuhan Institute of Technology;Wuhan 430074 |
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| Abstract: | Hydrogenation of styrene catalyzed by TpRuH(PPh3)(CH3CN) [Tp=hydrotris(pyrazolyl)borate] with THF,H2O/THF,CH3CN/THF and ROH/THF(R=Me,Et,iso-Pr,tert-Bu) as solvents was studied,re-spectively.It was found that addition of trace amount of small molecule H2O,CH3CN or ROH in anhydrous THF effectively promoted the catalytic reaction.The catalytic mechanism is proposed that PPh3 ligand in TpRuH(PPh3)(CH3CN) is first replaced by H2O,CH3CN or ROH to form intermediates TpRuH(CH3CN)L(L=H2O,CH3CN or ROH) to reduce the ... |
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| Keywords: | styrene steric hindrance catalytic hydrogenation ruthenium hydride complex |
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