| 曾纪珺.FeCl3/磷酸三丁酯催化四氯化碳与氯乙烯的调聚反应：结构与活性[J].分子催化,2015,(1):1-8 |
| FeCl3/磷酸三丁酯催化四氯化碳与氯乙烯的调聚反应：结构与活性 |
| FeCl3/ tributyl phosphate complex as catalyst in telomerization of tetrachloromethane with chloroethylene: Structure and activity |
| 投稿时间：2015-01-04 修订日期：2015-01-30 |
| DOI： |
| 中文关键词: 调聚反应 四氯化碳 铁基催化剂 动力学 链式氧化还原机理 |
| 英文关键词:telomerization tetrachloromethane iron catalyst kinetics chain redox-catalytic mechanism |
| 基金项目:陕西省科技统筹创新工程计划项目（2012KTCL01-01） |
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| 中文摘要: |
| 以四氯化碳与氯乙烯的调聚反应为目标反应，研究了FeCl3/磷酸三丁酯（TBP）配合物在反应体系中的结构，并关联了其结构与催化活性。采用摩尔电导、红外光谱和紫外吸收光谱对配合物的结构进行表征，结果表明FeCl3/TBP配合物在四氯化碳溶剂中为加合物FeCl3(TBP)n（n=1, 2和3），配位数n由TBP与FeCl3的化学计量数决定。通过表观动力学实验研究了该配合物的催化反应活性，实验结果表明反应表观速率常数（kobs）随着TBP与FeCl3的摩尔比（r）的增大而增大，反应引发期（t0）随着r的增大而减小。假定反应遵循链式氧化还原机理，推导了kobs和t0的表达式，表达式和实验结果一致，均表明kobs只与配合物FeCl3(TBP)n的配位数和浓度有关。 |
| 英文摘要: |
| The FeCl3 complex of tributyl phosphate (TBP) ligand had been tested in telomerization of tetrachloromethane with chloroethylene promoted by Fe/FeCl3 redox catalyst. The structural of the FeCl3/TBP complex was investigated by molar conductance analysis, IR spectra and UV-vis spectra. In the reaction system, The FeCl3/TBP complex is FeCl3(TBP)n adduct, the coordination numbers of the adduct are 1, 2 and 3, which are equal to the stoichiometrie of TBP to FeCl3. Kinetic results showed that the apparent rate constant kobs increases gradually with the increase of
the molar ratio of TBP and FeCl3（r）, while the reaction induction period t0 is decreased gradually with the increase of r. Assuming that the telomerization reaction follows a chain redox-catalytic mechanism, the expressions of kobs and t0 are derived, the expressions are consistent with the experimental data, and the expression and experimental data all show that the kobs is related with the coordination number and concentration of FeCl3(TBP)n complexes. |
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