Generation and EPR Spectroscopy of the First Silenyl Radicals, R2C=Si.−R: Experiment and Theory

Daniel Pinchuk, Yosi Kratish, Jomon Mathew, Lieby Zborovsky, Dmitry Bravo-Zhivotovskii, Boris Tumanskii*, Yitzhak Apeloig

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

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 languageEnglish (US)
Pages (from-to)7435-7439
Number of pages5
JournalAngewandte Chemie - International Edition
Volume58
Issue number22
DOIs
StatePublished - May 27 2019
Externally publishedYes

Keywords

  • EPR spectroscopy
  • metal-substituted silenes
  • silenyl radicals
  • silyl radicals
  • vinyl radicals

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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