CsF对Ni催化非端基炔烃与CO_2反应的影响的理论研究
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- 英文论文题名：The role of CsF in the coupling of internal alkyne and carbon dioxide catalyzed by Ni(cod)_2:A DFT study
- 论文作者：任丽娅 ; 李长玉 ; 丁万见
- 英文论文作者：Liya Ren ; Changyu Li ; Wanjian Ding ; Key Laboratory of Theoretical and Computational Photochemistry ; Ministry of Education ; College of Chemistry ; Beijing Normal University
- 年：2016
- 作者机构：北京师范大学化学学院理论及计算光化学教育部重点实验室;
- 论文关键词：炔烃 ; CO2 ; Ni催化 ; CsF
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第四十五分会：物理有机
- 语种：中文
- 分类号：O643.12
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十五分会 ; 物理有机
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：155k
- 原文格式：D
- 会议级别：全国
摘要
CO_2是主要的温室气体,同样是含量丰富、价格低廉的C1原料~1。近年来催化活化CO_2分子的研究受到了人们的广泛关注~(1-3)。本文对Ni(cod)_2催化下非端基炔烃二苯乙炔(PhCCPh)与CO_2的反应机理进行了详细的理论研究,并在此基础上考虑了CsF的作用。研究表明,PhCCPh与CO_2在Ni(cod)_2的存在下发生耦合反应能垒较高,反应较困难,CsF的加入能有效降低反应能垒。通过比较加入F-或CsF的反应机理,作者认为CsF主要通过F-与Ni的配位作用降低反应能垒。全文计算使用B3LYP泛函,配合混合基组(Cs原子使用SDD赝势及SDD基组,其他原子使用DGDZVP基组)进行。
The reaction mechanisms of PhCCPh and CO_2 mediated by Ni(cod)_2 under the presence of CsF were detailed investigated theoretically by using the B3 LYP functional in combination with basis set of SDD for the valence electrons of Cs and SDD pseudo-potential for the core electrons, and DGDZVP basis set for the other atoms. The results show that energy barrier for the rate-determining step of PhCCPh and CO_2 coupling mediated by Ni(cod)_2 is pretty high, suggesting that it is difficult to occur, while the presence of CsF could effectively decrease the energy barrier. By comparison of the mechanisms under the presence of F-and CsF, it is believed that the coordination of F-to Ni atom plays an important role to decrease the energy barrier.
The reaction mechanisms of PhCCPh and CO_2 mediated by Ni(cod)_2 under the presence of CsF were detailed investigated theoretically by using the B3 LYP functional in combination with basis set of SDD for the valence electrons of Cs and SDD pseudo-potential for the core electrons, and DGDZVP basis set for the other atoms. The results show that energy barrier for the rate-determining step of PhCCPh and CO_2 coupling mediated by Ni(cod)_2 is pretty high, suggesting that it is difficult to occur, while the presence of CsF could effectively decrease the energy barrier. By comparison of the mechanisms under the presence of F-and CsF, it is believed that the coordination of F-to Ni atom plays an important role to decrease the energy barrier.
引文
[1]Li,S.H.;Yuan,W.M.;Ma,S.M.Angew.Chem.Int.Ed.2011,50:2578.
[2]Shimizu,K.;Takimoto,M.;Sato,Y.;Mori,M.Org.Lett.2005,7:195.
[3]Li,J.;Jia,G.C.;Lin,Z.Y.Organomet.2008,27:3892.
[2]Shimizu,K.;Takimoto,M.;Sato,Y.;Mori,M.Org.Lett.2005,7:195.
[3]Li,J.;Jia,G.C.;Lin,Z.Y.Organomet.2008,27:3892.