title: Exploring the Reactivity Trends in the E2 and SN2 Reactions of X(-) + CH3CH2Cl (X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3).
abstract: The reactivity order of 12 anions toward ethyl chloride has been investigated by using the G2(+) method, and the competitive E2 and SN2 reactions are discussed and compared. The reactions studied are X(-) + CH3CH2Cl → HX + CH2═CH2 + Cl(-) and X(-) + CH3CH2Cl → CH3CH2X + Cl(-), with X = F, Cl, Br, HO, HS, HSe, NH2 PH2, AsH2, CH3, SiH3, and GeH3. Our results indicate that there is no general and straightforward relationship between the overall barriers and the proton affinity (PA) of X(-); instead, discernible linear correlations only exist for the X's within the same group of the periodic table. Similar correlations are also found with the electronegativity of central atoms in X, deformation energy of the E2 transition state (TS), and the overall enthalpy of reaction. It is revealed that the electronegativity will significantly affect the barrier height, and a more electronegative X will stabilize the E2 and SN2 transition states. Multiple linear regression analysis shows that there is a reasonable linear correlation between E2 (or SN2) overall barriers and the linear combination of PA of X(-) and electronegativity of the central atom.
authors.affiliation: Department of Biology and Chemistry, City University of Hong Kong, Kowloon, Hong Kong, College of Chemistry, Key Laboratory of Green Chemistry and Technology, Ministry of Education, and Key State Laboratory of Biotherapy, Sichuan University, Chengdu 610064, People's Republic of China, and Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong.
authors.forename: Xiao-Peng
authors.initials: XP
authors.lastname: Wu
authors.affiliation: Department of Biology and Chemistry, City University of Hong Kong, Kowloon, Hong Kong, College of Chemistry, Key Laboratory of Green Chemistry and Technology, Ministry of Education, and Key State Laboratory of Biotherapy, Sichuan University, Chengdu 610064, People's Republic of China, and Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong.
authors.forename: Xiao-Ming
authors.initials: XM
authors.lastname: Sun
authors.affiliation: Department of Biology and Chemistry, City University of Hong Kong, Kowloon, Hong Kong, College of Chemistry, Key Laboratory of Green Chemistry and Technology, Ministry of Education, and Key State Laboratory of Biotherapy, Sichuan University, Chengdu 610064, People's Republic of China, and Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong.
authors.forename: Xi-Guang
authors.initials: XG
authors.lastname: Wei
authors.affiliation: Department of Biology and Chemistry, City University of Hong Kong, Kowloon, Hong Kong, College of Chemistry, Key Laboratory of Green Chemistry and Technology, Ministry of Education, and Key State Laboratory of Biotherapy, Sichuan University, Chengdu 610064, People's Republic of China, and Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong.
authors.forename: Yi
authors.initials: Y
authors.lastname: Ren
authors.affiliation: Department of Biology and Chemistry, City University of Hong Kong, Kowloon, Hong Kong, College of Chemistry, Key Laboratory of Green Chemistry and Technology, Ministry of Education, and Key State Laboratory of Biotherapy, Sichuan University, Chengdu 610064, People's Republic of China, and Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong.
authors.forename: Ning-Bew
authors.initials: NB
authors.lastname: Wong
authors.affiliation: Department of Biology and Chemistry, City University of Hong Kong, Kowloon, Hong Kong, College of Chemistry, Key Laboratory of Green Chemistry and Technology, Ministry of Education, and Key State Laboratory of Biotherapy, Sichuan University, Chengdu 610064, People's Republic of China, and Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong.
authors.forename: Wai-Kee
authors.initials: WK
authors.lastname: Li