THIOCARBONYL VERSUS CARBONYL-COMPOUNDS - A COMPARISON OF INTRINSIC REACTIVITIES

The first systematic comparison of structural effects on the intrinsic reactivities of carbonyl and thiocarbonyl compounds has been carried out. To this end, the gas-phase basicities (GB) of a wide variety of thiocarbonyl compounds XCSY (as well as of some carbonyl derivatives) were determined by means of Fourier transform ion cyclotron resonance spectrometry (FTICR) and SCF and MP2 ab initio calculations at different levels of accuracy were performed on 27 different neutral compounds and their protonated forms. The same set, enlarged by the inclusion of very large systems such as di-tert-butyl- and bis-(1-adamantyl)thioketones was also investigated at the AM1 semiempirical level in order to get a more complete view of structural effects. The agreement between the calculated and the experimental changes in thermodynamic state functions is good in all instances. Correlation analysis of the experimental data shows that (i) substituent effects on the gas-phase basicity of thiocarbonyl compounds are linearly related to those of their carbonyl homologs with a slope of 0.80 and (ii) these effects can be quantitatively analyzed in terms of polarizability, field, and resonance effects (Taft-Topsom model). Comparison of the GBs of thiocarbonyl and carbonyl compounds with solution basicities and nucleophilicities sheds light on differential structural and solvation effects. Substituent effects on both neutral and protonated species were explored by means of appropriate isodesmic reactions. These results confirm that all thiocarbonyl compounds investigated are sulfur bases in the gas phase. The features revealed by correlation analysis can be rationalized in terms of the interactions between the MOs of the substituent and the parent compound.