Mechanism of the Thermal ZE Isomerization of a Stable Silene; Experiment and Theory

Lieby Zborovsky, Arseni Kostenko, Dmitry Bravo-Zhivotovskii, Yitzhak Apeloig

Research output: Contribution to journalArticlepeer-review

Abstract

The E and Z geometric isomers of a stable silene (tBu2MeSi)(tBuMe2Si)Si=CH(1-Ad) (1) were synthesized and characterized spectroscopically. The thermal Z to E isomerization of 1 was studied both experimentally and computationally using DFT methods. The measured activation parameters for the 1Z⇌1E isomerization are: Ea=24.4 kcal mol−1, ΔH=23.7 kcal mol−1, ΔS=−13.2 e.u. Based on comparison of the experimental and DFT calculated (at BP86-D3BJ/def2-TZVP(-f)//BP86-D3BJ/def2-TZVP(-f)) activation parameters, the Z⇌E isomerization of 1 proceeds through an unusual (unprecedented for alkenes) migration–rotation–migration mechanism (via a silylene intermediate), rather than through the classic rotation mechanism common for alkenes.

Original languageEnglish
Pages (from-to)14524-14528
Number of pages5
JournalAngewandte Chemie - International Edition
Volume58
Issue number41
DOIs
StatePublished - 7 Oct 2019

Keywords

  • DFT calculations
  • E-Z isomerization
  • kinetic studies
  • reaction mechanism
  • silenes

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Catalysis

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