Abstract
The first two persistent silenyl radicals (R2C=Si.−R), with a half-life (t1/2) of about 30 min, were generated and characterized by electron paramagnetic resonance (EPR) spectroscopy. The large hyperfine coupling constants (hfccs) (a(29Siα)=137.5–148.0 G) indicate that the unpaired electron has substantial s character. DFT calculations, which are in good agreement with the experimentally observed hfccs, predict a strongly bent structure (∡C=Si−R=134.7–140.7°). In contrast, the analogous vinyl radical, R2C=C.−R (t1/2≈3 h), exhibits a small hfcc (a(13Cα)=26.6 G) and has a nearly linear geometry (∡C=C−R=168.7°).
Original language | English |
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Pages (from-to) | 7435-7439 |
Number of pages | 5 |
Journal | Angewandte Chemie - International Edition |
Volume | 58 |
Issue number | 22 |
DOIs | |
State | Published - 27 May 2019 |
Keywords
- EPR spectroscopy
- metal-substituted silenes
- silenyl radicals
- silyl radicals
- vinyl radicals
All Science Journal Classification (ASJC) codes
- General Chemistry
- Catalysis