金属连二硫烯络合物分离烯烃的理论研究
文献类型：学位论文
| 作者 | 韩清珍 |
| 学位类别 | 博士 |
| 答辩日期 | 2008-06-10 |
| 授予单位 | 中国科学院过程工程研究所 |
| 授予地点 | 过程工程研究所 |
| 导师 | 温浩 |
| 关键词 | 金属连二硫烯 烯烃分离 溶剂效应 温度效应 分子结构效应 |
| 其他题名 | Theoretical Study on Olefin Separation by Dithiolene Complexes of Transition Metals |
| 学位专业 | 应用化学 |
| 中文摘要 | 过渡金属连二硫烯络合物以其独特的结构和性质引起了人们的广泛关注，至今已在有机导体、超导体、磁性材料、三阶非线性光学材料、近红外激光材料、氧化还原剂等方面获得成功的应用。过渡金属连二硫烯络合物以其与烯烃、二烯烃以及炔烃的络合作用在烯烃分离方面显示出潜在的应用价值。 本论文采用密度泛函理论系统研究了过渡金属连二硫烯络合物与烯烃的反应机理、溶剂效应、温度效应和对烯烃的选择性，在此基础上，进一步探索过渡金属连二硫烯络合物的分子结构对其反应机理和反应特性的影响。主要研究工作及创新成果如下： 1）系统研究了镍连二硫烯与烯烃的反应机理和溶剂效应，并探索了反应的温度效应。结果表明，溶剂极性增强能促进镍连二硫烯与烯烃的反应，降低反应的活化能，加快反应速度，增加产物产率。另外，研究发现该反应是放热反应，标准态下当温度低于335 K时反应能自发进行，温度升高，反应速度加快，但产物产率降低，不利于络合反应的进行。 2）对镍连二硫烯与其他单烯烃的反应进行了系统地分析，研究了镍连二硫烯对单烯烃的选择性。结果表明，当烯烃结构复杂性增加时，镍连二硫烯与烯烃反应的速度减慢，产物产率降低。相同溶剂中，镍连二硫烯对结构简单的烯烃具有良好的选择性，且对顺反异构的烯烃也具有一定的选择性。 3）探索了端基取代基和中心金属对金属连二硫烯与乙烯反应的影响。研究结果表明：端基取代基电负性增强能加快反应速度，增加产物产率，促进反应的发生。另外，中心金属决定着络合物的分子几何构型，并能改变其与乙烯反应的反应历程。其中，平面结构的Fe、Ni和Au连二硫烯络合物与C2H4的反应是两步反应，第一步反应是反应的决速步；而四面体结构的Cu和Ag连二硫烯络合物与C2H4的反应是一步反应。在Fe、Ni、Cu、Ag和Au的金属连二硫烯络合物中，Ni的连二硫烯络合物与C2H4反应的产物最稳定，产率最高。 |
| 英文摘要 | Nowadays the dithiolene complexes of transition metals have attracted much more attention due to their particular structures and characteristics. They have been successfully applied in many fields, such as organic conductors, superconductors, magnetic materials, third-order nonlinear optical materials, near infrared waveband laser materials, oxidation-reduction agents, and so forth. In addition, the transition metal dithiolene complexes have shown potential value of applications in the separation of olefins for their coordination with olefins, dialkenes, and alkynes. In this dissertation, we systematically studied the mechanisms of the reaction between transition metal dithiolene and olefins, the solvent effects, the temperature effects and the selectivity by means of density functional theory. Furthermore, we considered the influences of the dithiolene molecular structures on the reaction mechanisms and the reaction properties. The main content and innovative contributions of this dissertation are shown in the following: 1) The mechanism of the reaction between Ni dithiolene and olefins, the solvent effects, and the temperature effects are systematically studied. It is shown that the reaction of complexing olefins with Ni dithiolene may occur much easier and faster with a higher product rate when the polarity of the solvent becomes larger. Moreover, the results indicate that the reaction is a continually exothermic process. In the standard state, the reaction will occur spontaneously when the temperature is under 335K. As the temperature increases, the equilibrium of chemical reaction will shift left with a faster reaction speed and a lower product rate. 2) The selectivity of the Ni dithiolene is also investigated by systematical analyzing the reactions between Ni dithiolene and eight kinds of olefins. It is demonstrated that, as the structure complexity of the olefins increases, the reaction rate constant and the equilibrium constant will decrease. Therefore, we may draw that the nickel dithiolene has a good selectivity of the olefins with simple structures and with trans-structures in certain solvents. 3) The influences induced by the terminal substituents and the central transition metals on the reaction between Ni dithiolene and olefins are theoretically explored. It is shown that, as the electronegativities of the substituents increase, both the rate constants and the equilibrium constants will increase, which is favorable for the reaction. In addition, the central metal can play a decisive role on the structure of dithiolene and even change the mechanism of the reaction between ethylene and dithiolene. It is also found that the reaction between plane structure dithiolene of Fe, Ni, and Au with ethylene should be a two-step process, and the first step is the rate-determining step. However, the reaction of the tetrahedral dithiolene is a one-step process. Moreover, the product of the reaction between Ni dithiolene and ethylene is the most stable and the corresponding product rate is the highest in the reactions of adding ethylene to Fe, Ni, Cu, Ag, and Au dithiolene. |
| 语种 | 中文 |
| 公开日期 | 2013-09-13 |
| 页码 | 152 |
| 源URL | [http://ir.ipe.ac.cn/handle/122111/1125]  |
| 专题 | 过程工程研究所_研究所（批量导入） |
| 推荐引用方式 GB/T 7714 | 韩清珍. 金属连二硫烯络合物分离烯烃的理论研究[D]. 过程工程研究所. 中国科学院过程工程研究所. 2008. |
入库方式： OAI收割
来源：过程工程研究所
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