Addition of nucleophiles to silenes. A theoretical study of the effect of substituents on their kinetic stability

Michael Bendikov, Sabine Ruth Quadt, Oded Rabin, Yitzhak Apeloig

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

The addition of water to nine silenes (H2Si=CH2 (1), Me2Si=C(SiH3)2 (2), Cl2Si=CH2 (3), Me2Si=CMe2 (4), (H3Si)2Si=CMe2 (5), (H3Si)2Si=C(Me)OSiH3 (6), Me2Si=C(SiMe3)H (7), Me(HCC)Si=CH2 (8), and Me(Me3Si)Si=CH2 (9)) was studied with ab initio (MP4/6-31+G(d,p)) and DFT (B3LYP/6-31G(d)) methods. The energy barriers for addition, which denote the kinetic stability of the silene, strongly depend on the substituents. Silenes (1-4) exhibit low and even negative activation energies (-3 to 8 kcal/mol). Substituents that strongly reduce the polarity of the silene, as in 5 and 6, increase significantly the activation energy for the nucleophilic addition of H2O to ca. 16 kcal/mol. The calculated activation energies show a good correlation with Δt (Δt = the difference in the total NBO charge between Si and C), i.e., the higher the polarity of the silene the lower is the activation barrier for water addition.

Original languageEnglish
Pages (from-to)3930-3939
Number of pages10
JournalOrganometallics
Volume21
Issue number19
DOIs
Publication statusPublished - Sep 16 2002

Fingerprint

Nucleophiles
nucleophiles
Activation energy
Kinetics
kinetics
activation energy
polarity
Water
Energy barriers
Discrete Fourier transforms
Chemical activation
water
activation
energy

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Addition of nucleophiles to silenes. A theoretical study of the effect of substituents on their kinetic stability. / Bendikov, Michael; Quadt, Sabine Ruth; Rabin, Oded; Apeloig, Yitzhak.

In: Organometallics, Vol. 21, No. 19, 16.09.2002, p. 3930-3939.

Research output: Contribution to journalArticle

Bendikov, Michael ; Quadt, Sabine Ruth ; Rabin, Oded ; Apeloig, Yitzhak. / Addition of nucleophiles to silenes. A theoretical study of the effect of substituents on their kinetic stability. In: Organometallics. 2002 ; Vol. 21, No. 19. pp. 3930-3939.
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