DFT calculations of the neighboring groups effects on cheletropic reaction of 2,5-Dihydrothiophene sulfone

In this research DFT calculations were used to investigate the neighboring effects on cheletropic reaction of 2,5-Dihydrothiophene sulfone(1). Structural properties and stereoelectronic behavior in the activation energy and enthalpy of cheletropic reaction was performed for 2,5-Dihydrothiophene sulfone where substitutions of CF3; CCl3 and CBr3 that were placed on Sulfolen were investigated by using DFT-B3LYP/6-311+G** level of theory. The Results of calculations using B3LYP, HF and MP2 [basic 6-311+G**] showed that the trend of electronic effects on the cis and trans state is different. Reaction rate and activation energy in cis compounds showed that increasing electronegativity and decreasing the band length reduced the reaction speed. Trend of reaction rate and activation energy in Trans compounds showed that in cheletropic reaction rate and activation energy not only electronic effects but also the Steric effects play a main role. DFT/B3LYP/6-311+G** calculation results also confirm these results. In cis compounds, 2,5- three Floro metyl Sulfolen(2) has the highest activation energy about (12.25 kcal/mol) and the lowest rate of reaction. In trans compounds, Trans-2,5- three chloro metyl Sulfolen(7) has the highest activation energy about (12.99 kcal/mol) and the lowest rate of reaction.

Keywords:

DFT , cheletropy , 2 , 5-Dihydrothiophene sulfone , NBO , stereo-electronic effect