Raman and infrared spectra, conformational stability, barriers to internal rotation, vibrational assignment, and ab initio calculations of 3-methyl-3-butenenitrile

Abstract

The Raman (3500–30 cm −1) spectra of liquid and solid and the infrared (3500–40 cm −1) spectra of gaseous and solid 3-methyl-3-butenenitrile, CH 2 C(CH 3)CH 2C N, have been recorded. Both cis and gauche conformers have been identified in the fluid phases but only the cis form remains in the solid. Variable temperature (−55 to −100 °C) studies of the infrared spectra of the sample dissolved in liquid xenon have been carried out. From these data, the enthalpy difference has been determined to be 163±16 cm −1 (1.20±0.19 kJ mol −1), with the cis conformer the more stable rotamer. It is estimated that there is 48±2% of the gauche conformer present at 25°C. A complete vibrational assignment is proposed for the cis conformer based on infrared band contours, relative intensities, depolarization ratios and group frequencies. Several of the fundamentals for the gauche conformer have also been identified. The vibrational assignments are supported by normal coordinate calculations utilizing ab initio force constants. Complete equilibrium geometries have been obtained for both rotamers by ab initio calculations employing the 6-31G(d), 6-311G(d,p), 6-311+G(d,p) and 6-311+G(2d,2p) basis sets at the levels of restricted Hartree–Fock (HF) and/or Møller–Plesset perturbation theory to the second order (MP2). Only with the 6-311G(2d,2p) and 6-311G(2df,2pd) basis sets with or without diffuse functions is the cis conformer predicted to be more stable than the gauche form. The potential energy terms for the conformational interchange have been obtained at the MP2(full)/6-311+G(2d,2p) level, and compared to those obtained from the experimental data. The results are discussed and compared to the corresponding quantities obtained for some similar molecules.