ROTATIONAL-ISOMERISM IN CH3C(=S-SCH3 AND CH3C(=S)-S-CH2CH3 - A COMBINED VIBRATIONAL SPECTROSCOPIC AND AB-INITIO STUDY

Rotational isomerism in CH3C(=S)SCH3 and CH3C(=S)SCH2CH3 is examined b y combining a vibrational spectroscopic with an ab initio MO study. Pa rticular emphasis is given to the gauche half arrow pointing right ove r half arrow pointing left anti conformational equilibrium originated by internal rotation about the dithioester S-CH2CH3 bond in CH3C(=S)SC H2CH3. The ab initio equilibrium geometries of the molecules studied a re calculated by gradient geometry refinement, and the conformational dependence of some relevant structural parameters is used to character ize the most important intramolecular interactions present in the vari ous conformers. For ethyl dithioacetate, correlation between the calcu lated and the observed frequencies for the condensed phases and the is olated molecule clearly shows that the most stable form corresponds to the non-symmetric s-cis/gauche form (the ab initio calculated values of the relevant dihedral angles are 0-degrees (S=C-SC) and almost-equa l-to +/-84-degrees (CS-CC)). Variable temperature Raman experiments sh ow that the enthalpy difference between the s-cis/gauche and s-cis-ant i forms is 1.9 +/- 0.2 kJ mol-1. Observed frequency shifts for vS-C an d vC-S are successfully correlated with substitution of the alkyl and acyl fragments. A consistent interpretation of the resonance Raman spe ctra of both methyl and ethyl dithioacetate and their isotopomers is a lso achieved.