Density functional theory investigation of electrophilic addition reaction of chlorine to tricyclo[4.2.2.2(2,5)]dodeca-1,5-diene


Abbasoglu R. , YAŞAR A.

TURKISH JOURNAL OF CHEMISTRY, cilt.34, ss.127-134, 2010 (SCI İndekslerine Giren Dergi) identifier identifier

  • Cilt numarası: 34 Konu: 1
  • Basım Tarihi: 2010
  • Doi Numarası: 10.3906/kim-0812-14
  • Dergi Adı: TURKISH JOURNAL OF CHEMISTRY
  • Sayfa Sayıları: ss.127-134

Özet

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.