Density functional theory investigation of electrophilic addition reaction of chlorine to tricyclo[4.2.2.22,5 ]dodeca-1,5-diene

Rza ABBASOĞLU; Ahmet YAŞAR

Makale detayları

Density functional theory investigation of electrophilic addition reaction of chlorine to tricyclo[4.2.2.22,5 ]dodeca-1,5-diene

Yazarlar:

Rza ABBASOĞLU | Ahmet YAŞAR

Yayıncı:

TUBITAK

Ana Başlıklar:

Uygulamalı fizik

Dergi:

Turkish Journal of Chemistry 2010 Vol.34 Issue 1, pp.127-134

Belge Tipi:

Makale

Yayın Tarihi:

12/2009

Belge Dili:

İngilizce

Document ID (Org No.):

2000728158

Sıklık:

İki Aylık

eISSN:

1303-6130

pISSN:

1300-0527

Özet:

 

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.

 

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.

Makale detayları

Density functional theory investigation of electrophilic addition reaction of chlorine to tricyclo[4.2.2.22,5 ]dodeca-1,5-diene

Yazarlar: Rza ABBASOĞLU | Ahmet YAŞAR

Yayıncı: TUBITAK

Ana Başlıklar: Uygulamalı fizik

Dergi: Turkish Journal of Chemistry 2010 Vol.34 Issue 1, pp.127-134

Belge Tipi: Makale

Yayın Tarihi: 12/2009

Belge Dili: İngilizce

Document ID (Org No.): 2000728158

Sıklık: İki Aylık

eISSN: 1303-6130

pISSN: 1300-0527

Sayı

Yazarlar:

Rza ABBASOĞLU | Ahmet YAŞAR

Yayıncı:

TUBITAK

Ana Başlıklar:

Uygulamalı fizik

Dergi:

Turkish Journal of Chemistry 2010 Vol.34 Issue 1, pp.127-134

Belge Tipi:

Makale

Yayın Tarihi:

12/2009

Belge Dili:

İngilizce

Document ID (Org No.):

2000728158

Sıklık:

İki Aylık

eISSN:

1303-6130

pISSN:

1300-0527