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 : 20 | Download : 8

Publication Date : 0000-00-00

Article Type : Research Paper

Abstract :Potential energy surface insert ignore into journalissuearticles values(PES); of the tricyclo[4.2.2.22,5]dodeca- 1,5-diene insert ignore into journalissuearticles values(TCDD);-Cl2 system was studied by B3LYP/6-311+Ginsert ignore into journalissuearticles values(d,p); method and the configurations [reactants, molecular charge-transfer insert ignore into journalissuearticles values(CT); complex, transition states insert ignore into journalissuearticles values(TS1 and TS2);, intermediate insert ignore into journalissuearticles values(INT);, and product insert ignore into journalissuearticles values(P);] corresponding to the stationary points insert ignore into journalissuearticles values(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 insert ignore into journalissuearticles values(INT); with energy 14.682 kcal mol-1 higher than that of the CT-complex. The intermediate insert ignore into journalissuearticles values(INT); then transforms easily insert ignore into journalissuearticles values(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