A comparative ab initio study of methyl formate, methyl thiolformate and methyl thionoformate

Abstract

Ab initio SCF-MO calculations have been carried out for HCOOCH 3, HC(O)SCH 3 and HC(S)OCH 3. Relative stabilities of s-trans/s-cis conformers are reported and discussed in terms of specific intramolecular interactions. The energy difference between the s-trans and the s-cis form increases in the order methyl thiolformate < methyl thionoformate < methyl formate. The major stabilizing factors of the s-cis forms are the bond dipolar interaction and the mesomeric delocalization through the five member ring involving both the XCYC (X, Y  O, S) skeleton and the out-of-plane hydrogen atoms. These effects are used to explain the trends mentioned. The non-planarity previously proposed for the thionoester is reinvestigated. Our calculations show that this molecule is planar. Molecular atomic charges, dipole moments and ionisation potentials are determined and compared with available experimental values.