Negative Hyperconjugation versus Electronegativity: Vibrational Spectra of Free Fluorinated Alkoxide Ions in the Gas Phase

Authors
Publication date 2015
Journal ChemPhysChem
Volume | Issue number 16 | 9
Pages (from-to) 1992-1995
Organisations
  • Faculty of Science (FNWI) - Van 't Hoff Institute for Molecular Sciences (HIMS)
Abstract CO stretching frequencies of free, gaseous, fluorinated alkoxide ions shift substantially to the blue, relative to those of corresponding alcohols complexed with ammonia. Free -fluorinated ions, pentafluoroethoxide and heptafluoroisopropoxide anions, display further blue shifts relative to cases with only -fluorination, providing experimental evidence for fluorine negative hyperconjugation. DFT analysis with the atoms in molecules (AIM) method confirms an increase in CO bond order for the -fluorinated ions, demonstrating an increase in carbonyl character for the free ions.
Document type Article
Note With supporting information
Language English
Published at https://doi.org/10.1002/cphc.201500177
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