有机过渡金属化合物反应体系的理论研究

【作者】 刘阳；

【导师】 王长生；

【作者基本信息】 辽宁师范大学 ， 有机化学， 2003， 硕士

【摘要】 本文采用密度泛函理论B3LYP方法对有机过渡金属化合物参与的化学反应体系进行了理论研究。探讨反应机理，寻找反应的过渡态，优化反应物、产物及中间体的几何构型，计算各个构型的单点能和频率。本论文主要研究了以下三个反应体系。1)对Me₃W（≡CH） + O₂ Me₂W（=O）（=CH₂） + HCHO的反应机理进行了研究。设计了可能发生的反应途径，优化得到了反应物、反应的过渡态、中间体、产物的几何构型，讨论了各反应途径发生的难易程度。2)以有机过渡金属钨化合物中的α-氢转移反应体系为研究对象，通过对一系列氢转移反应的研究，探讨了不同位置上不同取代基对反应活化能的影响。同时，我们还研究了不同过渡金属（铬、钼、钨）对α-氢转移反应活化能的影响。3)对丙烯腈和丙烯在有机钼化合物催化下的反应机理进行了研究。讨论了各个反应途径进行的难易程度及其对应产物的稳定性。更多还原

【Abstract】 Based on density functional theory (DFT) and B3LYP method, we made a theoretical study of the reaction system involving organic transitional metal compound. We studied the mechanism of each reaction. We determined the structure of the reactants，intermediates, products and transition states, and discussed the change of the structures in all the reactions. The single point energy and frequency of each structure was calculated. Three different organic transitional metal compound systems had been studied.Chapter one mainly deals with the reaction between organic transitional metal tungsten compound and oxygen. To find the most probable reaction path, we made a theoretical analysis of the reaction between Me3WCH and oxygen. We designed three schemes corresponding to different mechanisms, and made hypothesizes of the possible intermediates and products. By comparing and analyzing the results of different paths we at last found the most probable reaction path.In the second chapter, we studied a seriesα-hydrogen shift reaction in organic transitional metal tungsten compound The purpose is to find out the most preferable substitutes that can lower the active energy to a largest extent. At the same time, we changed the central transitional metal to study its effects on active energy.The last chapter is about the reaction between CH2CHCN and CH2CHMe under the catalysis of organic transitional metal molybdenum compound. We studied the mechanisms of the reaction and made a thorough analysis of the results from both the dynamical and thermodynamical point. At last we find the best way in each step and obtained the active energy of each step. Meanwhile, we draw some other important conclusion.更多还原