TY - JOUR
T1 - Theoretical study of the addition of hydrogen halides to olefins: A comparison between (HCl)2 and (HF)2 additions to ethylene
AU - Clavero, Carmen
AU - Duran, Miquel
AU - Lledós, Agustí
AU - Ventura, Oscar N.
AU - Bertrán, Juan
PY - 1987/1/1
Y1 - 1987/1/1
N2 - The addition of HCl and (HCl)2 to ethylene is theoretically studied by means of ab initio SCF techniques using the 3‐21G basis set. A statistical thermodynamics analysis is also carried out. When a comparison is made with the HF and (HF)2 additions to ethylene, the general fact of the catalytic action of the second HX molecule in the (HX)2 complex is revealed. The behavior of HF, however, is very different from that of HCl, since in the former case the driving force in the termolecular transition state is the bonding between fluorine and carbon, while in the latter case the driving force is the bonding between carbon and hydrogen, as generally accepted for electrophilic reactions. The use of density plots of the transition states on the plane of the cycle allows us to conclude that, while both HF and HCl termolecular transition states are hexacyclic, the bimolecular transition state of the HCl addition is bicentric and not tetracentric as previously reported. Copyright © 1987 John Wiley & Sons, Inc.
AB - The addition of HCl and (HCl)2 to ethylene is theoretically studied by means of ab initio SCF techniques using the 3‐21G basis set. A statistical thermodynamics analysis is also carried out. When a comparison is made with the HF and (HF)2 additions to ethylene, the general fact of the catalytic action of the second HX molecule in the (HX)2 complex is revealed. The behavior of HF, however, is very different from that of HCl, since in the former case the driving force in the termolecular transition state is the bonding between fluorine and carbon, while in the latter case the driving force is the bonding between carbon and hydrogen, as generally accepted for electrophilic reactions. The use of density plots of the transition states on the plane of the cycle allows us to conclude that, while both HF and HCl termolecular transition states are hexacyclic, the bimolecular transition state of the HCl addition is bicentric and not tetracentric as previously reported. Copyright © 1987 John Wiley & Sons, Inc.
U2 - 10.1002/jcc.540080428
DO - 10.1002/jcc.540080428
M3 - Article
VL - 8
SP - 481
EP - 488
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
SN - 0192-8651
IS - 4
ER -