On the association of frustrated Lewis pairs in ionic liquids: a molecular dynamics simulation study
文献类型：期刊论文
| 作者 | Liu, Xiaoqing1; Wang, Xiaojing1; Li, Yao2; Yu, Tianhao2; Zhao, Weizhen2; Liu, Lei2 |
| 刊名 | PHYSICAL CHEMISTRY CHEMICAL PHYSICS
 |
| 出版日期 | 2021-05-03 |
| 页码 | 8 |
| ISSN号 | 1463-9076 |
| DOI | 10.1039/d1cp00479d |
| 英文摘要 | Sterically hindered frustrated Lewis pairs (FLPs) have the ability to activate hydrogen molecules, and their reactivity is strongly determined by the geometric parameters of the Lewis acids and bases. A recent experimental study showed that ionic liquids (ILs) could largely improve the effective configuration of FLPs. However, the detailed mechanistic profile is still unclear. Herein, we performed molecular dynamics (MD) simulations to reveal the effects of ILs on the structures of FLPs, in particular, the association of Lewis acids and bases. For this purpose, mixed systems were adopted consisting of the ILs [C(n)mim][NTf2] (n = 6, 10, 14), [C(6)mim][PF6] and [C(6)mim][CTf3] and the typical FLP (tBu)(3)P/B(C6F5)(3) for MD simulations. Radial distribution functions (RDFs) results show that toluene competes with (tBu)(3)P to interact with B(C6F5)(3), resulting in a relatively low effective (tBu)(3)P/B(C6F5)(3) complex, while [C(10)mim][NTf2] shows less competition with (tBu)(3)P, which increases the amount of effective FLPs. Spatial distribution functions (SDFs) results show that toluene forms a continuum solvation-shell, which hinders the interactions between (tBu)(3)P and B(C6F5)(3), while [C(10)mim][NTf2] leaves relatively large empty spaces, which are accessible for (tBu)(3)P or B(C6F5)(3) molecules, resulting in higher probabilities of effective FLP structures. Lastly, we find that the longer alkyl chain length of [C(n)mim](+) cations, the higher the amount of effective (tBu)(3)P/B(C6F5)(3) pairs, and the anion [CTf3](-) shows negative effects, for which even less effective (tBu)(3)P/B(C6F5)(3) pairs have been found compared to those of toluene. |
| WOS关键词 | HYDROGEN ACTIVATION ; ORBITAL METHODS ; FORCE-FIELD ; DENSITY ; MECHANISM ; THERMOCHEMISTRY ; REACTIVITY ; CHEMISTRY ; MIXTURES ; ELEMENTS |
| 资助项目 | National Natural Science Foundation of China[21978294] ; National Natural Science Foundation of China[51901209] ; National Natural Science Foundation of China[21808224] |
| WOS研究方向 | Chemistry ; Physics |
| 语种 | 英语 |
| WOS记录号 | WOS:000651131900001 |
| 出版者 | ROYAL SOC CHEMISTRY |
| 资助机构 | National Natural Science Foundation of China |
| 源URL | [http://ir.ipe.ac.cn/handle/122111/48782]  |
| 专题 | 中国科学院过程工程研究所 |
| 通讯作者 | Liu, Xiaoqing; Liu, Lei |
| 作者单位 | 1.North Univ China, Sch Environm & Safety Engn, Taiyuan 030051, Peoples R China 2.Chinese Acad Sci, Beijing Key Lab Ion Liquids Clean Proc, Inst Proc Engn, Key Lab Green Proc & Engn, Beijing 100190, Peoples R China |
| 推荐引用方式 GB/T 7714 | Liu, Xiaoqing,Wang, Xiaojing,Li, Yao,et al. On the association of frustrated Lewis pairs in ionic liquids: a molecular dynamics simulation study[J]. PHYSICAL CHEMISTRY CHEMICAL PHYSICS,2021:8. |
| APA | Liu, Xiaoqing,Wang, Xiaojing,Li, Yao,Yu, Tianhao,Zhao, Weizhen,&Liu, Lei.(2021).On the association of frustrated Lewis pairs in ionic liquids: a molecular dynamics simulation study.PHYSICAL CHEMISTRY CHEMICAL PHYSICS,8. |
| MLA | Liu, Xiaoqing,et al."On the association of frustrated Lewis pairs in ionic liquids: a molecular dynamics simulation study".PHYSICAL CHEMISTRY CHEMICAL PHYSICS (2021):8. |
入库方式： OAI收割
来源：过程工程研究所
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