THEORETICAL INVESTIGATION OF SUBSTITUTION EFFECT ON THE PROTON TRANSFER MECHANISM IN 3-MERCAPTO-PROPENETHIAL

Abstract

We present detailed theoretical studies of the proton transfer (PT) in the 3-Mercaptopropenethial (MP) and in some of its derivatives. The e®ect of substitution on the transition state structures corresponding to the PT in R2 or R1(3) positions is studied by using B3LYP/6- 311þþG** level of theory in gas phase and water solution. The following substituents have been taken into consideration: Cl, F, OH, SH, OCH3, SCH3, CHO, NO2, CCH and OCF3. For the di®erent derivatives of 3-MP, we have computed geometries and potential energy curves for the intramolecular PT in their ground. Also, the excited-state properties of intramolecular hydrogen bonding in substituted systems have been investigated theoretically using the timedependent density functional theory method. The -electron delocalization parameter (Q) and HOMA index as a geometrical indicator of a local aromaticity are investigated. Natural bond orbital (NBO) analysis was also performed for better understanding the nature of intramolecular interactions. The results of analysis by Quantum theory of \Atoms in Molecules" and NBO method fairly support the DFT results. Correlations between the PT reaction barrier versus topological parameters, (SH) and (SH) are also probed. The obtained results showed a strong in°uence of the R substituent on the PT reaction barrier changes. Numerous correlations between topological, geometrical, thermodynamic properties and energetic parameters were also found.