Asymmetric identity SN2 transition states: Nucleophilic substitution at α-substituted carbon and silicon centers

Registro completo de metadados
MetadadosDescriçãoIdioma
Autor(es): dc.creatorRocha, Marcus V. J.-
Autor(es): dc.creatorSmits, Nicole W. G.-
Autor(es): dc.creatorWolters, Lando P.-
Autor(es): dc.creatorCózar, Abelde-
Autor(es): dc.creatorGuerra, Célia Fonseca-
Autor(es): dc.creatorRamalho, Teodorico C.-
Autor(es): dc.creatorBickelhaupt, F. Matthias-
Data de aceite: dc.date.accessioned2026-02-09T11:34:05Z-
Data de disponibilização: dc.date.available2026-02-09T11:34:05Z-
Data de envio: dc.date.issued2019-09-26-
Data de envio: dc.date.issued2019-09-26-
Data de envio: dc.date.issued2017-02-
Fonte completa do material: dc.identifierhttps://repositorio.ufla.br/handle/1/36940-
Fonte completa do material: dc.identifierhttps://www.sciencedirect.com/science/article/pii/S1387380616300872-
Fonte: dc.identifier.urihttp://educapes.capes.gov.br/handle/capes/1142541-
Descrição: dc.descriptionWe 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.-
Idioma: dc.languageen-
Publicador: dc.publisherElsevier-
Direitos: dc.rightsrestrictAccess-
???dc.source???: dc.sourceInternational Journal of Mass Spectrometry-
Palavras-chave: dc.subjectDensity functional calculations-
Palavras-chave: dc.subjectNucleophilic substitution-
Palavras-chave: dc.subjectSilicon-
Palavras-chave: dc.subjectSubstituent effects-
Palavras-chave: dc.subjectReaction mechanisms-
Título: dc.titleAsymmetric identity SN2 transition states: Nucleophilic substitution at α-substituted carbon and silicon centers-
Tipo de arquivo: dc.typeArtigo-
Aparece nas coleções:Repositório Institucional da Universidade Federal de Lavras (RIUFLA)

Não existem arquivos associados a este item.