Publication
Title
Spectra and structure of organophosphorus compounds XLV : vibrational spectra, conformational stability, ab initio calculations, and vibrational assignment of chloromethyl difluorophosphine and chloromethyl
Author
Abstract
The IR (4000-50 cm-1) and Raman (4000-20 cm-1) spectra of chloromethyl difluorophosphine, ClCH2PF2, and chloromethyl difluorophosphine-d2, ClCD2PF2, in the vapor (293 K) and solid phases (77 K) have been recorded. Additionally, the Raman (4000-50 cm-1) spectra of the liquid phase of these compounds along with qualitative depolarization ratios have also been obtained. These data have been interpreted on the basis of an equilibrium between trans (chlorine atom trans to phosphorus lone pair) and gauche conformers in the gas and liquid phases. Vapor phase IR contours along with the solvent and temperature effects have allowed the assignment of conformer doublet components to the individual conformers. From the study of the Raman spectrum of the liquid as a function of temperature a value of 167 +/-25 cm-1 (2.0 +/- 0.3 kJ mol-1) has been determined for the enthalpy difference, with the trans rotamer more stable than the gauche conformer. In the vapor phase the gauche conformer strongly dominates, whereas the crystalline solid obtained at 77 K consists exclusively of the trans conformer. A complete vibrational assignment for both conformers of each isotopomer, based on IR contours, Raman depolarization data, group frequencies and normal coordinate calculations is proposed. The conformational stabilities, barriers to internal rotation, force constants and fundamental vibrational frequencies, along with the structural parameters, have been obtained from ab initio Hartree-Fock gradient calculations employing both the RHF/3-21G* and RHF/6-31G* basis sets.
Language
English
Source (journal)
Journal of molecular structure. - Amsterdam
Publication
Amsterdam : 1992
ISSN
0022-2860
Volume/pages
272(1992), p. 305-346
ISI
A1992JU77900019
Full text (Publisher's DOI)
Full text (publisher's version - intranet only)
UAntwerpen
Faculty/Department
Research group
Publication type
Subject
Affiliation
Publications with a UAntwerp address
External links
Web of Science
Record
Identification
Creation 08.10.2008
Last edited 08.07.2017
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