Cycloaddition reactions of silacyclopropylidenoids to ethylene
Yükleniyor...
Tarih
2018
Yazarlar
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
ACG Publications
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
The cycloaddition reactions of silacyclopropylidenoids (C2H4SiXLi, X = F, Cl, Br) to ethylene have been investigated separately to gain insights into halogen and solvation effects on the energetic of the proposed reactions at the B3LYP/6-311+G(d, p) level of theory. The calculations reveal that the addition of silacyclopropylidenoids to ethylene occurs via stepwise mechanisms. The required initial energy barriers for the conversion of silacyclopropylidenoids to silaspiropentanes are determined to be ?G = 77.4 kJ/mol, 9.6 kJ/mol, and 9.2 kJ/mol for F, Cl, and Br, respectively. Furthermore, the gas phase calculations show that the reactions are not spontaneous at room temperature, whereas those of THF solvated models indicate that the formations of silaspiropentanes are spontaneous in the cases of X = Br and Cl. Additionally, the findings show that the silacyclopropylidene addition to ethylene is determined to be exergonic in both gas and THF phases by ?G = - 42.6 kJ/mol and -39.3 kJ/mol, respectively. © 2018 ACG Publications. All rights reserved.
Açıklama
Anahtar Kelimeler
DFT, Reaction Mechanism, Silacyclopropylidenoids, Silaspiropentane, Silylenoid
Kaynak
Organic Communications
WoS Q Değeri
N/A
Scopus Q Değeri
Q3
Cilt
11
Sayı
1
