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 language | English |
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Pages (from-to) | 14524-14528 |
Number of pages | 5 |
Journal | Angewandte Chemie - International Edition |
Volume | 58 |
Issue number | 41 |
DOIs | |
State | Published - 7 Oct 2019 |
Keywords
- DFT calculations
- E-Z isomerization
- kinetic studies
- reaction mechanism
- silenes
All Science Journal Classification (ASJC) codes
- General Chemistry
- Catalysis