Microsolvation effects on the reactivity of oxy-nucleophiles: the case of gas-phase SN2 reactions of YO-(CH3OH) n=1,2 towards CH3Cl

Journal of Molecular Modeling
Liu Yun-YunLau Kai-Chung

Abstract

The modified G4(MP2) method was applied to explore microsolvation effects on the reactivity of four solvated normal oxy-nucleophiles YO-(CH3OH) n=1,2 (Y = CH3, C2H5, FC2H4, ClC2H4), and five α-oxy-nucleophiles YO-(CH3OH) n=1,2 (Y = HO, CH3O, F, Cl, Br), in gas-phase SN2 reactions towards the substrate CH3Cl. Based on a Brønsted-type plot, our calculations reveal that the overall activation barriers of five microsolvated α-oxy-nucleophiles are obviously smaller than the prediction from the correlation line constructed by four normal microsolvated ones to different degrees, and clearly demonstrate the existence of an α-effect in the presence of one or two methanol molecule(s). Moreover, it was found that the α-effect of the mono-methanol microsolvated α-nucleophile is stronger than that of the monohydrated α-nucleophile. However, the α-effect of YO-(CH3OH)2 becomes weaker for Y = HO and CH3O, whereas it becomes stronger for Y = F, Cl, Br than that of YO-(H2O)2, which can be explained by analyses of the activation strain model in the two cases. It was also found that the rationale about the low ionization energy of α-nucleophile inducing the α-effect was not widely significant. Graphical abstract Variation of alpha-effect in the g...Continue Reading

References

May 18, 2000·The Journal of Organic Chemistry·I H Um, E Buncel
Aug 11, 2005·Journal of Computational Chemistry·A Patrícia BentoF Matthias Bickelhaupt
Dec 31, 2005·Organic Letters·Yi Ren, Hiroshi Yamataka
Sep 30, 2006·Chemistry : a European Journal·Yi Ren, Hiroshi Yamataka
Oct 10, 2006·The Journal of Organic Chemistry·Eric V Patterson, K R Fountain
Jun 26, 2007·The Journal of Organic Chemistry·Yi Ren, Hiroshi Yamataka
Oct 2, 2007·The Journal of Chemical Physics·Larry A CurtissKrishnan Raghavachari
Aug 12, 2008·The Journal of Organic Chemistry·A Patrícia Bento, F Matthias Bickelhaupt
May 22, 2009·Journal of the American Chemical Society·Stephanie M VillanoVeronica M Bierbaum
Oct 22, 2009·Journal of the American Chemical Society·Xin ChenJohn I Brauman
May 22, 2010·Organic & Biomolecular Chemistry·Willem-Jan van Zeist, F Matthias Bickelhaupt
Aug 13, 2011·Journal of the American Chemical Society·John M GarverVeronica M Bierbaum
Jun 21, 2013·Journal of Computational Chemistry·Yi RenWai-Kee Li
Sep 21, 2013·Journal of the American Chemical Society·Ditte L ThomsenVeronica M Bierbaum
Oct 15, 2013·The Journal of Physical Chemistry. a·Ditte L ThomsenVeronica M Bierbaum
Dec 19, 2013·Journal of the American Society for Mass Spectrometry·Ditte L ThomsenVeronica M Bierbaum
Jan 20, 2015·Nature Communications·István Szabó, Gábor Czakó
Mar 12, 2015·Journal of Computational Chemistry·Wen-Yang ZhaoKai-Chung Lau
Apr 2, 2016·Science·Jing Xie, William L Hase

❮ Previous
Next ❯

Citations

Nov 5, 2021·Physical Chemistry Chemical Physics : PCCP·Subhasish Mallick, Pradeep Kumar

❮ Previous
Next ❯

Related Concepts

Related Feeds

Adhesion Molecules in Health and Disease

Cell adhesion molecules are a subset of cell adhesion proteins located on the cell surface involved in binding with other cells or with the extracellular matrix in the process called cell adhesion. In essence, cell adhesion molecules help cells stick to each other and to their surroundings. Cell adhesion is a crucial component in maintaining tissue structure and function. Discover the latest research on adhesion molecule and their role in health and disease here.

Cell Adhesion Molecules in the Brain

Cell adhesion molecules found on cell surface help cells bind with other cells or the extracellular matrix to maintain structure and function. Here is the latest research on their role in the brain.