Yang Ming-Chung, Sharma Akhilesh K, Sameera W M C, Morokuma Keiji, Su Ming-Der
Department of Applied Chemistry, National Chiayi University , Chiayi 60004, Taiwan.
Fukui Institute for Fundamental Chemistry, Kyoto University , Kyoto 606-8103, Japan.
J Phys Chem A. 2017 Apr 6;121(13):2665-2673. doi: 10.1021/acs.jpca.7b01086. Epub 2017 Mar 24.
The addition reaction of M(Cl)(CO)(PPh) (M = Rh, Ir) and M(PPh) (M = Pd, Pt) fragments with X@C (X = 0, Li) were characterized by density functional theory (DFT) and the artificial force-induced reaction (AFIR) method. The calculated free energy profiles suggested that the η[6:6]-addition is the most favorable reaction, which is consistent with the experimental observations. In the presence of Li ion, the reaction is highly exothermic, leading to η[6:6] product of LIrLi@C. In contrast, an endothermic reaction was observed in the absence of a Li ion. The encapsulated Li ion can enhance the thermodynamic stability of the η[6:6] product. The energy decomposition analysis showed that the interaction between metal fragment and X@C fragment is the key for the thermodynamic stability. Among the group IA and IIA metal cations, Be encapsulation is the best candidate for the development of new fullerene-transition metal complexes, which will be useful for future potential applications such as solar cells, catalysts, and electronic devices.
通过密度泛函理论（DFT）和人工力诱导反应（AFIR）方法对M(Cl)(CO)(PPh)（M = Rh、Ir）和M(PPh)（M = Pd、Pt）片段与X@C（X = O、Li）的加成反应进行了表征。计算得到的自由能剖面图表明，η[6:6]加成是最有利的反应，这与实验观察结果一致。在锂离子存在下，反应是高度放热的，生成LIrLi@C的η[6:6]产物。相比之下，在没有锂离子的情况下观察到吸热反应。封装的锂离子可以提高η[6:6]产物的热力学稳定性。能量分解分析表明，金属片段与X@C片段之间的相互作用是热力学稳定性的关键。在IA族和IIA族金属阳离子中，铍封装是开发新型富勒烯-过渡金属配合物的最佳候选者，这将对未来诸如太阳能电池、催化剂和电子器件等潜在应用有用。
