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高等学校化学研究 ›› 2005, Vol. 21 ›› Issue (2): 217-219.

• Articles • 上一篇    下一篇

Effects of Anions and Cations on π-Complexation Between Olefin and Metal Halide

ZHOU Jin-xia, ZHANG Yong-chun, GUO Xin-wen   

  1. State Key Laboratory of Fine Chemical, Dalian University of Technology, Dalian 116012, P. R. China
  • 收稿日期:2004-04-29 出版日期:2005-03-24 发布日期:2011-07-27

Effects of Anions and Cations on π-Complexation Between Olefin and Metal Halide

ZHOU Jin-xia, ZHANG Yong-chun, GUO Xin-wen   

  1. State Key Laboratory of Fine Chemical, Dalian University of Technology, Dalian 116012, P. R. China
  • Received:2004-04-29 Online:2005-03-24 Published:2011-07-27

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摘要： An ab initio molecular orbital study was performed to determine the effects of anions and cations on the π-complexation of C2H4 on MX(M=Ag, Cu; X=F, Cl).The calculated results show the following order of adsorption strength: F-＞Cl- for anions; Cu+＞Ag+ for cations.The results can be explained by the detailed analysis of atomic charge, orbital energy and orbital population by using the natural bond orbital(NBO) theory: (1) anions with stronger electronegativity can attract more electrons from the s orbital of M, while at the same time it does not obviously weaken the d orbital occupation of M, thus the nearly vacant s orbital and the sufficiently filled d orbitals of M help with forming σ-donation and d-π* backdonation with the π orbital and the π* orbital of olefin, respectively; (2) a smaller energy gap of symmetry-adapted orbitals between olefin and a cation can favor the electron transfer, that is why Cu+ forms stronger adsorption with olefin than Ag+ does.

关键词: π-Complexation, ab initio Calculation, Olefin, Anion, Cation

Abstract: An ab initio molecular orbital study was performed to determine the effects of anions and cations on the π-complexation of C2H4 on MX(M=Ag, Cu; X=F, Cl).The calculated results show the following order of adsorption strength: F-＞Cl- for anions; Cu+＞Ag+ for cations.The results can be explained by the detailed analysis of atomic charge, orbital energy and orbital population by using the natural bond orbital(NBO) theory: (1) anions with stronger electronegativity can attract more electrons from the s orbital of M, while at the same time it does not obviously weaken the d orbital occupation of M, thus the nearly vacant s orbital and the sufficiently filled d orbitals of M help with forming σ-donation and d-π* backdonation with the π orbital and the π* orbital of olefin, respectively; (2) a smaller energy gap of symmetry-adapted orbitals between olefin and a cation can favor the electron transfer, that is why Cu+ forms stronger adsorption with olefin than Ag+ does.

Key words: π-Complexation, ab initio Calculation, Olefin, Anion, Cation