Infrared and microwave spectra, molecular conformation and electric dipole moment of methyl thiolformate

Abstract

The microwave spectrum (41-10 GHz) and the infrared spectrum (4000-50 cm −1) of methyl thiolformate have been obtained and analyzed. The spectra are consistent with a single molecular conformation having a planar array of heavy atoms and with the alkyl group cis to the carbonyl group. The measured rotational constants are: A, 11042.22 MHz; B, 5118.27 MHz; C, 3562.03 MHz (κ = −0.5839). No internal rotation doublets were observed in the microwave spectrum for the ground vibrational state, which implies that the barrier hindering internal rotation of the methyl group is either much larger or much smaller than the corresponding value for methyl formate. If the former is true then a lower limit of 10.5 kJ mol −1 may be placed on the barrier height. The dipole moment of methyl thiolformate was measured using the Stark effect to be 1.58 ± 0.05 Debyes ( μ A = 1.52 D; μ B = 0.43 D) for the vapor, and for dilute solutions in benzene at 295 K the value of 1.6 ± 0.1 D was found from capacitance measurements. SCF computations using minimal basis sets of STO 3G atomic orbitals and extended basis sets of STO 4.31G atomic orbitals have been carried out for methyl thiolformate and methyl formate. Energy differences between rotational isomers and estimates of barrier heights are given together with the calculated dipole moments.