Some Geometric and Electronic Structural Effects of Perfluorinating Propionyl Chloride

Author

Garry S. Grubbs, Missouri University of Science and TechnologyFollow
Robert A. Powoski
D. Jojola
Stephen A. Cooke

Abstract

Propionyl chloride and perfluoropropionyl chloride have been characterized using chirped pulse Fourier transform microwave spectroscopy between the frequency range of 8 and 14 GHz. Molecules were studied in separate experiments in supersonic expansions of argon. the ³⁵Cl, ³⁷Cl, and each of the monoisotopic ¹³C substituted isotopologues of propionyl chloride were observed. the ³⁵Cl and ³⁷Cl isotopologues of perfluoropropionyl chloride were observed. Analyses of the resulting microwave spectra have yielded spectroscopic constants for the target molecules. the analyses indicate that, under the conditions of these experiments, both molecules are only detectable as cis conformers in which aCCCO = 0°. Comparisons are made between the electronic and geometric structure of propionyl chloride and perfluoropropionyl chloride, and also other acyl chlorides. the data produced are relevant in regards to quantifying the known destabilizing effect of perfluoroalky chains on carbonyl groups. Distinct differences in electronegativity between the CH₃CH₂CO- and CF ₃CF₂CO- groups are discussed. Methyl group internal rotation is observed for propionyl chloride and has been analyzed to produce a V₃ barrier height.

Recommended Citation

G. S. Grubbs et al., "Some Geometric and Electronic Structural Effects of Perfluorinating Propionyl Chloride," Journal of Physical Chemistry A, vol. 114, no. 30, pp. 8009 - 8015, American Chemical Society (ACS), Jan 2010.

The definitive version is available at https://doi.org/10.1021/jp103966e

Department(s)

Chemistry

International Standard Serial Number (ISSN)

1089-5639

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2010 American Chemical Society (ACS), All rights reserved.

Publication Date

01 Jan 2010