MOLECULAR-STRUCTURES OF CIS-S-ETHYL AND TRANS-S-ETHYL THIOCROTONATE -A COMBINED VIBRATIONAL SPECTROSCOPIC AND AB-INITIO SCF-MO STUDY

Ab initio 6-31G SCF-MO calculations have been carried out for cis- an d trans-S-ethyl thiocrotonate [cis- and trans- CH3-CH=CH-C(=O)SCH2CH3] . Fully optimized geometries, relative stabilities, dipole moments and harmonic force fields for several conformers of these molecules have been determined and the results compared with those of similar molecul es. Combined with FTIR spectroscopic data, the theoretical results dem onstrate that trans-S-ethyl thiocrotonate exists in two different conf ormations about the C alpha-C bond (the s-cis and s-trans forms, with C=C-C=O dihedral angles equal to 0 degrees and 180 degrees, respective ly), the s-cis conformation being more stable than the s-trans form by ca. 7 kJ mol(-1) for the isolated molecule situation, while the cis-s -ethyl thiocrotonate molecule adopts only the s-cis conformation about this bond. A comparison of the experimental and theoretical vibration al spectra also shows that the existence of the less stable s-trans is omer of an alpha,beta-unsaturated thioester can be successfully monito red by the IR band at ca. 1165 cm(-1), ascribed to the C alpha-C stret ching mode of this form. Additional conformationally sensitive bands a re also identified, but these are difficult to use in the IR spectrum because of overlap with other features.