Turkish Journal of Chemistry
DOI
10.3906/kim-0812-14
Abstract
Potential energy surface (PES) of the tricyclo[4.2.2.2^{2,5}]dodeca- 1,5-diene (TCDD)-Cl_2 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 Cl_2 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 [4.2.2.2^{2, 5}]dodeca-1, 5-diene.
First Page
127
Last Page
134
Recommended Citation
ABBASOĞLU, RZA and YAŞAR, AHMET
(2010)
"Density functional theory investigation of electrophilic addition reaction of chlorine to tricyclo[4.2.2.2^{2,5}]dodeca-1,5-diene,"
Turkish Journal of Chemistry: Vol. 34:
No.
1, Article 13.
https://doi.org/10.3906/kim-0812-14
Available at:
https://journals.tubitak.gov.tr/chem/vol34/iss1/13
