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.
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 reaction has three possible channels, namely, π channel, σ channel and ,π＋σ channel, and the π＋σ channel is the most major channel due to the lowest activation energy barrier. Furthermore, under the presence of high CO pressures, the complexes Cl2Pt（CO）2 and Cl2Pt（CO）PH3, which are fromed by Cl2Pt（PH3）2, can behave as an ＂active＂ catalytic species, and the similar π＋σ channel is the most favorable channel.
出处
《西北师范大学学报（自然科学版）》
CAS
北大核心
2010年第1期55-61,89,共8页
Journal of Northwest Normal University(Natural Science)
基金
甘肃省自然科学基金资助项目(0710RJZ114)
甘肃省教育厅研究生导师基金资助项目(0801-10)
关键词
氯代丙烯
羰基化
铂类化合物
密度泛函理论
allyl chloride
carbonylation
platinum complexes
density functional theory
