Asymmetric Identity SN2 Transition States: Nucleophilic Substitution at alpfa-Substituted Carbon and Silicon Centers

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F62690094%3A18450%2F17%3A50005101" target="_blank" >RIV/62690094:18450/17:50005101 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1016/j.ijms.2016.06.003" target="_blank" >http://dx.doi.org/10.1016/j.ijms.2016.06.003</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.ijms.2016.06.003" target="_blank" >10.1016/j.ijms.2016.06.003</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Asymmetric Identity SN2 Transition States: Nucleophilic Substitution at alpfa-Substituted Carbon and Silicon Centers

Popis výsledku v původním jazyce

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 ZORAOLYP/ TZ2P. Our purpose is twofold. We wish to understand: (i) how the alpha-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.

Název v anglickém jazyce

Asymmetric Identity SN2 Transition States: Nucleophilic Substitution at alpfa-Substituted Carbon and Silicon Centers

Popis výsledku anglicky

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 ZORAOLYP/ TZ2P. Our purpose is twofold. We wish to understand: (i) how the alpha-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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

30107 - Medicinal chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2017

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

International journal of mass spectrometry

ISSN

1387-3806

e-ISSN

—

Svazek periodika

413

Číslo periodika v rámci svazku

SI

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

7

Strana od-do

85-91

Kód UT WoS článku

000399264900011

EID výsledku v databázi Scopus

2-s2.0-84977513049