- Turkish Journal of Chemistry
- Vol: 34 Issue: 1
- Density functional theory investigation of electrophilic addition reaction of chlorine to tricyclo[4...
Density functional theory investigation of electrophilic addition reaction of chlorine to tricyclo[4.2.2.22,5 ]dodeca-1,5-diene
Authors : Rza Abbasoğlu, Ahmet Yaşar
Pages : 127-134
View : 11 | Download : 6
Publication Date : 9999-12-31
Article Type : Makaleler
Abstract :Potential energy surface (PES) of the tricyclo[4.2.2.22,5]dodeca- 1,5-diene (TCDD)-Cl2 system was studied by B3LYP/6-311+G(d,p) method and the configurations [reactants, molecular charge-transfer (CT) complex, transition states (TS1 and TS2), intermediate (INT), and product (P)] corresponding to the stationary points (minima or saddle points) were determined. Initially, a molecular CT-complex forms between Cl2 and TCDD. With a barrier of 22.362 kcal mol-1 the CT-complex can be activated to an intermediate (INT) with energy 14.682 kcal mol-1 higher than that of the CT-complex. The intermediate (INT) then transforms easily (barrier 5.102 kcal mol-1) into the final, N-type product. Accompanying the breaking of the Cl-Cl bond, C1-Cl, C5-Cl and C2-C6 bonds are formed, and C1=C2 and C5=C6 double bonds transform into single bonds. The direction of the reaction is determined by the direction of the intramolecular skeletal rearrangement that is realized by the formation of the C2-C6 bond.Keywords : DFT calculations, intrinsic reaction coordinates, transannular reactions, tricyclo [4.2.2.22, 5]dodeca-1, 5-diene.