Use este identificador para citar ou linkar para este item: http://repositorio.ufla.br/jspui/handle/1/36940
Título: Asymmetric identity SN2 transition states: Nucleophilic substitution at α-substituted carbon and silicon centers
Palavras-chave: Density functional calculations
Nucleophilic substitution
Silicon
Substituent effects
Reaction mechanisms
Data do documento: Fev-2017
Editor: Elsevier
Citação: 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.
Resumo: 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
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