Citation: ZHAO Dong-Bo, RONG Chun-Ying, JENKINS Samantha, KIRK Steven R., YIN Du-Lin, LIU Shu-Bin. Origin of the cis-Effect: a Density Functional Theory Study of Doubly Substituted Ethylenes[J]. Acta Physico-Chimica Sinica, ;2013, 29(01): 43-54. doi: 10.3866/PKU.WHXB201211121 shu

Origin of the cis-Effect: a Density Functional Theory Study of Doubly Substituted Ethylenes

1.
1 Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China) and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha 410081, P. R. China;
2 Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420, U. S. A.

Received Date: 21 August 2012
Available Online: 12 November 2012
Fund Project: 杰出人才项目(23040609)资助 (23040609) 赵东波受湖南省研究生创新项目(CX2012B223)资助 (CX2012B223)

It is well known that the trans isomer of a doubly substituted ethylene is more stable than its cis counterpart because of the more favorable electrostatic and steric interactions in the trans conformer. Exceptions do exist nevertheless. 1,2-Difluoroethylene is such an example, so is 1,2-dichloroethylene. The unusual stability of the cis isomer of these doubly substituted ethylene compounds is referred to as the cis-effect, whose nature and origin are still not well understood. In this work, using 12 simple molecules, XHC=CHY (X, Y=F, Cl, Br, CN, CH₃, OCH₃, C₂H₆), as examples, we perform systematic studies to investigate the validity, nature, and origin of this effect. Among the systems studied, 9 of them exhibit the existence of the cis-effect and the remaining 3 systems are conventional systems used for the comparison purpose. We employ a large number of density functionals and basis sets to confirm its validity. We also use a few well-established analysis tools, such as natural bond orbital (NBO), energy decomposition analysis (EDA), density functional reactivity theory (DFRT), and non-covalent interaction (NCI) analysis, to pinpoint its nature and origin. We found that there exists a weak but attractive non-covalent interaction between the two substituting groups in the cis conformer. We also found that electrostatic, steric, and kinetic energies all play important roles for the validity of the cis-effect. Nevertheless, none of these quantities can be solely used as the single reason verning the general validity of the cis-effect, suggesting that the origin of the effect is complicated and its validity results from compound interactions from a number of interactions. In this work, we employ two-variable explanations to justify its validity through the electrostatic interaction plus steric effect or kinetic energy, with which reasonable fits with R²=0.86-0.87 were obtained.
- Density functional theory,
- cis-Effect,
- Natural bond orbital analysis,
- Steric effect,
- Non-covalent interaction
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