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

doi:10.1021/om0202571

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

Weizmann Institute of Science, Israel

Research output: Contribution to journal › Article › peer-review

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 language	English
Pages (from-to)	3930-3939
Number of pages	10
Journal	Organometallics
Volume	21
Issue number	19
DOIs	https://doi.org/10.1021/om0202571
Publication status	Published - Sep 16 2002

ASJC Scopus subject areas

Inorganic Chemistry
Organic Chemistry

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

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.",

author = "Michael Bendikov and Quadt, {Sabine Ruth} and Oded Rabin and Yitzhak Apeloig",

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AU - Bendikov, Michael

AU - Quadt, Sabine Ruth

AU - Rabin, Oded

AU - Apeloig, Yitzhak

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