过渡金属连二硫烯配合物电子构型和离域特性对其性质的影响
文献类型：学位论文
| 作者 | 孙丽丽 |
| 学位类别 | 博士 |
| 答辩日期 | 2011-06-07 |
| 授予单位 | 中国科学院研究生院 |
| 导师 | 温浩 |
| 关键词 | 金属连二硫烯 共轭二烯烃 溶剂效应 光电性质 分子结构 |
| 其他题名 | The Effect of Electron Configuration and Delocalization on the Properties of Transition Metal Dithiolenes |
| 学位专业 | 应用化学 |
| 中文摘要 | 过渡金属连二硫烯配合物具有优异的光电学性质，并且与烯烃的反应性质有用于烯烃分离的前景。这些性质与其独特的电子构型和离域特性密切相关。本论文采用密度泛函方法考察了不同取代基团和中心金属原子对其电子构型的影响，进而对离子化能，电子亲和势，重组能，以及电子吸收光谱的影响。研究了取代基以及溶剂对镍连二硫烯与共轭二烯烃反应体系的电荷分布，分子轨道，及反应动力学和热力学性质的影响，主要研究工作和创新成果如下： 1）研究了不同取代基和金属原子对连二硫烯配合物光谱学和电子迁移性质的影响。Ni(S2C2R2)2 (R = −NO2, −CN, −CF3, −F, −H, −CH3, −C2H5)的离子化能和电子亲和势随取代基吸电子能力的增强而增大；当取代基与连二硫烯形成共轭时，能降低分子的重组能。M(S2C2H2)2 (M = Ni, Pd, Pt, Cu, Ag, Au)均具有较高的电子亲和势和较低的电子重组能，有利于电子的注入和传输。金属连二硫烯配合物从基态到第一电子激发态的电子跃迁主要是配体到配体的跃迁并包含少量的金属到配体的跃迁或者配体到金属的跃迁。 2）对Ni[S2C2(CF3)2]2与顺-2-丁烯或丁二烯可能存在的反应路径进行了多方面的探索，通过计算反应的热力学函数，发现Ni[S2C2(CF3)2]2与顺-2-丁烯的配体间加成和配体内加成都是最有可能发生的反应路径。Ni[S2C2(CF3)2]2与丁二烯在配体的配体间加成和和配体内加成均有可能发生。在反应的过程中，Ni[S2C2(CF3)2]2中的电子由离域化向定域化的转变。 3）研究了镍连二硫烯与共轭二烯烃的取代基效应和溶剂效应。结果表明，镍连二硫烯与丁二烯的反应是亲电加成反应，在镍连二硫烯上引入吸电子基团（−CN，−CF3），在丁二烯上引入供电子基团（−CH3）有利于反应的进行。溶剂极性增强更加有利于丁二烯向Ni[S2C2(CF3)2]2转移电子，降低反应的能垒，促进反应的进行。 |
| 英文摘要 | The transition metal dithiolenes exhibit excellent spectral and electrical property. Moreover, the reactivity between transition metal dithiolenes and olefins shows potential in olefin separation. These property correlates with their special electron configuration and delocalization property. In this dissertation, we investigated the influence of substituents and metal atoms on their electron configuration, and then on their ionization energy, the electron affinity, reorganization energy and their electron absorption spectra using density functional theory. We also studied the reactions of nickel dithiolenes with conjugated dienes. We investigated the influence of substituents and solvent effect on the charge distribution and molecular orbital, and then on their dynamical and thermodynamical reaction property by density functional theory. The main content and innovative contributions of this dissertation are shown in the following: 1) The influence induced by the terminal substituents and the central transition metals on the spectral and electrical transfer properties of dithiolene complexes is investigated. It is shown that, as the electron-withdrawing ability of the substituents increase, both the ionization energy and the electron affinity of nickel dithiolene will increase. The reorganization energy becomes lower when the subtituents are conjugated with dithiolenes. M(S2C2H2)2 (M = Ni, Pd, Pt, Cu, Ag, Au) all show higher electron affinity and lower electron reorganization energy, so it is easy for the electrons to inject and transfer. The electron transition from the ground state to the first excited state is mainly ligand to ligand charge transfer (LLCT), and a little metal to ligand charge transfer (MLCT) or ligand to metal charge transfer (LMCT). 2) The possible reaction routes between Ni[S2C2(CF3)2]2 and cis-2-butylene or butadiene were also investigated. It is demonstrated by thermodynamical property analysis that both the interligand addition and intraligand addition between Ni[S2C2(CF3)2]2 and cis-2-butylene are possible to occur. Both the interligand addition and the intraligand reaction between Ni[S2C2(CF3)2]2 and butadiene are possible to occur. During the reaction process, the electrons of Ni[S2C2(CF3)2]2 tend to localization from delocalization. 3) The substituent effect and solvent effect on the reaction of nickel dithiolenes and conjugated dienes are also studied. It is shown that the reactions of nickel dithiolenes with conjugated dienes are electrophilic addition. It occurs much easier when electron-withdrawing groups (−CN, −CF3) are introduced to nickel dithiolenes or electron-donating group (−CH3) is introduced to butadiene. The electron transfer between butadiene and Ni[S2C2(CF3)2]2 becomes easier, the energy barrier becomes lower and it is more favorable for the reaction when the polarity of the solvent becomes larger. |
| 语种 | 中文 |
| 公开日期 | 2013-09-23 |
| 页码 | 113 |
| 源URL | [http://ir.ipe.ac.cn/handle/122111/1672]  |
| 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 | 孙丽丽. 过渡金属连二硫烯配合物电子构型和离域特性对其性质的影响[D]. 中国科学院研究生院. 2011. |
入库方式： OAI收割
来源：过程工程研究所
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