Please use this identifier to cite or link to this item: http://repositorio.ufla.br/jspui/handle/1/36940
Title: Asymmetric identity SN2 transition states: Nucleophilic substitution at α-substituted carbon and silicon centers
Keywords: Density functional calculations
Nucleophilic substitution
Silicon
Substituent effects
Reaction mechanisms
Issue Date: Feb-2017
Publisher: Elsevier
Citation: ROCHA, M. V. J. et al. Asymmetric identity SN2 transition states: Nucleophilic substitution at α-substituted carbon and silicon centers. International Journal of Mass Spectrometry, [S.l.], v. 413, p. 85-91, Feb. 2017.
Abstract: We have quantum chemically investigated the archetypal nucleophilic substitution reactions at carbon (SN2@C) and at silicon (SN2@Si) in the model reaction systems Cl− + A(CH3)2(CH2X)Cl (A = C, Si; X = H, F, Cl, Br, I) using relativistic density functional theory (DFT) at ZORA-OLYP/TZ2P. Our purpose is twofold. We wish to understand: (i) how the α-substituent X affects SN2 reactivity; and (ii) how methyl substituents at the central electrophilic atom A exactly participate in the transition vector of the Walden inversion. Interestingly, despite the fact that our SN2 model reactions are symmetric, i.e., constitute identity reactions, they proceed via slightly asymmetric transition states. We have also explored competing E2 pathways.
URI: https://www.sciencedirect.com/science/article/pii/S1387380616300872
http://repositorio.ufla.br/jspui/handle/1/36940
Appears in Collections:DQI - Artigos publicados em periódicos

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