title: The α-effect exhibited in gas-phase S(N)2@N and S(N)2@C reactions.
abstract: In order to explore the existence of α-effect in gas-phase S(N)2@N reactions, and to compare its similarity and difference with its counterpart in S(N)2@C reactions, we have carried out a theoretical study on the reactivity of six α-oxy-Nus (FO(-), ClO(-), BrO(-), HOO(-), HSO(-), H2NO(-)) in the S(N)2 reactions toward NR2Cl (R = H, Me) and RCl (R = Me, i-Pr) using the G2(+)M theory. An enhanced reactivity induced by the α-atom is found in all examined systems. The magnitude of the α-effect in the reactions of NR2Cl (R = H, Me) is generally smaller than that in the corresponding S(N)2 reaction, but their variation trend with the identity of α-atom is very similar. The origin of the α-effect of the S(N)2@N reactions is discussed in terms of activation strain analysis and thermodynamic analysis, indicating that the α-effect in the S(N)2@N reactions largely arises from transition state stabilization, and the "hyper-reactivity" of these α-Nus is also accompanied by an enhanced thermodynamic stability of products from the n(N) → σ*(O-Y) negative hyperconjugation. Meanwhile, it is found that the reactivity of oxy-Nus in the S(N)2 reactions toward NMe2Cl is lower than toward i-PrCl, which is different from previous experiments, that is, the S(N)2 reactions of NH2Cl is more facile than MeCl.
authors.affiliation: College of Chemistry and Key State Laboratory of Biotherapy, Sichuan University, Chengdu 610064, China. renyi@scu.edu.cn
authors.forename: Yi
authors.initials: Y
authors.lastname: Ren
authors.forename: Xi-Guang
authors.initials: XG
authors.lastname: Wei
authors.forename: Si-Jia
authors.initials: SJ
authors.lastname: Ren
authors.forename: Kai-Chung
authors.initials: KC
authors.lastname: Lau
authors.forename: Ning-Bew
authors.initials: NB
authors.lastname: Wong
authors.forename: Wai-Kee
authors.initials: WK
authors.lastname: Li
mesh_terms: D000838:Anions / Q000737:chemistry; D002244:Carbon / Q000737:chemistry; D004583:Electrons; D005740:Gases / Q000737:chemistry*; D009584:Nitrogen / Q000737:chemistry; D013816:Thermodynamics
chemical_list: D000838:Anions; D005740:Gases; D002244:Carbon; D009584:Nitrogen
keywords: NBO analysis; activation strain analysis; reactivity of oxy-nucleophile; α-effect in gas-phase SN2@N and SN2@C reactions