Reactivity of heavier vinyl anions [(CH3)2-rfeti=E'(CH3)]- (E, E' = C, Si, Ge) toward carbon monoxide: A computational study
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Tarih
2017
Yazarlar
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
American Chemical Society
Erişim Hakkı
info:eu-repo/semantics/closedAccess
Özet
The structures of heavier vinyl anions [(CH3)2E=E'(CH3)]- (E, E' = C, Si, Ge) and their abilities to activate carbon monoxide were investigated by DFT. Particularly, heteronuclear species exhibit a strong influence of the position of the heavier of the two group 14 elements (E or E') with strongly differing singlet-triplet gaps as a measure of tetrylene character. The reactions of CSi and CGe (E' = Si, Ge) with CO proceed in a concerted manner via [1 + 2] or [2 + 2] cycloadditions to a variety of potential products, whereas those of positional isomers as well as digerma and sila-germa analogues occur in a stepwise fashion. The three-membered rings derived from tetrylene-like vinyl anions (E' = Si, Ge and E = C) are dominated by keto resonance structures, while an enol structure is observed for the product obtained from SiC. Allene-like isomers could only be optimized in case of E = Si, Ge. © 2017 American Chemical Society.
Açıklama
Anahtar Kelimeler
Kaynak
Organometallics
WoS Q Değeri
N/A
Scopus Q Değeri
Q2
Cilt
36
Sayı
16
