| 铂类化合物催化氯代丙烯羰基化反应机理的理论研究 |
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| 引用本文： | 耿志远,孙小建,王永成,王玉芝,盛玉.铂类化合物催化氯代丙烯羰基化反应机理的理论研究[J].西北师范大学学报,2010,46(1):55-61,89. |
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| 作者姓名： | 耿志远 孙小建 王永成 王玉芝 盛玉 |
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| 作者单位： | 西北师范大学化学化工学院,甘肃省高分子材料重点实验室,甘肃兰州730070 |
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| 基金项目： | 甘肃省自然科学基金，甘肃省教育厅研究生导师基金 |
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| 摘 要： | 采用密度泛函理论,在B3LYP/6-311G**/RECP水平下对铂类化合物催化氯代丙烯的羰基化反应进行了理论计算研究,对势能面上各稳定点进行了全几何参数优化,通过频率分析确认了过渡态,并采用内禀反应坐标(IRC)进行了验证,用连续介质模型(PCM)计算了在CH2Cl2溶液中的溶剂化效应.结果表明,此标题反应有3条反应通道:π,σ和π+σ作用通道.比较发现,对于π+σ作用通道,反映在势能面上速控步的能垒最低,为标题反应的主反应通道.同时还发现当体系中的CO浓度增大时,活性催化体由Cl2Pt(PH3)2通过依次离去配体PH3生成Cl2Pt(CO)PH3和Cl2Pt(CO)2,其最有利的反应通道为类π+σ作用通道.
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| 关 键 词： | 氯代丙烯 羰基化 铂类化合物 密度泛函理论 |
Theoretical study of the mechanism of allyl chloride carbonylation catalyzed by platinum complexes |
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| GENG Zhi-yuan,SUN Xiao-jian,WANG Yong-cheng,WANG Yu-zhi,SHENG Yu.Theoretical study of the mechanism of allyl chloride carbonylation catalyzed by platinum complexes[J].Journal of Northwest Normal University Natural Science (Bimonthly),2010,46(1):55-61,89. |
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| Authors: | GENG Zhi-yuan SUN Xiao-jian WANG Yong-cheng WANG Yu-zhi SHENG Yu |
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| Institution: | GENG Zhi-yuan,SUN Xiao-jian,WANG Yong-cheng,WANG Yu-zhi,SHENG Yu(Key Laboratory of Polymer Materials of Gansu Province,College of Chemistry , Chemical Engineering,Northwest Normal University,Lanzhou 730070,Gansu,China) |
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| Abstract: | Using the B3LYP method of density functional theory,the reaction mechanism of platinum complexes catalyzed allyl alcohol carbonylation has been characterized in detail,while the geometries for all stationary points are completely optimized at the DFT-B3LYP/6-311G**/RECP level,and all the transition states are verified by the vibrational analysis and the intrinsic reaction coordinate calculations.Moreover,the effect of dichloromethane solvent is investigated by PCM method.The results indicate that the title ... |
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| Keywords: | allyl chloride carbonylation platinum complexes density functional theory |
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