Infrared and Raman spectra, ab initio calculations, conformational stability and vibrational assignment of 1-bromo-1-silacyclopentane

Abstract

Infrared and Raman spectra (3500–60 cm −1) of gas and/or liquid and solid 1-bromo-1-silacyclopentane (c-C 4H 8SiBrH) have been recorded and the vibrational data indicate the presence of a single conformer with no symmetry which is consistent with the twisted form. Ab initio calculations with a variety of basis sets up to MP2(full)/6-311+G(2df,2pd) predict the envelope-axial and envelope-equatorial conformers to be saddle points with nearly the same energies but approximately 900 cm −1 (5.98 kJ/mol) lower in energy than the planar conformer. Density functional theory calculations by the B3LYP method predict slightly lower energies for the two envelope forms and considerably lower energy for the planar form compared to the MP2 predictions. By utilizing the MP2(full)/6-31G(d) calculations the force constants, frequencies, infrared intensities, band contours, Raman activities, and depolarization values have been obtained to support the vibrational assignment. Estimated r 0 structural parameters have been obtained from adjusted MP2(full)/6-311+G(d,p) calculations. These experimental and theoretical results are compared to the corresponding quantities of some other five-membered rings.