Determination of Reactivities by Molecular Orbital Theory (VI). Sigma MO Treatment on $C_6H_5YCH_2Cl$

화학반응성의 분자궤도론적 연구 (제 6 보). $C_6H_5YCH_2Cl$ 형 화합물의 시그마분자궤도론적 고찰

  • Lee, Ikc-Hoon (Department of Chemistry, College of Science, Inha University) ;
  • Lee, Bon-Su (Department of Applied Chemistry, Seoul National University) ;
  • Lee, Jae-Eui (Department of Chemistry, College of Science, Inha University)
  • Published : 1974.04.30


Extended H ckel Theory and CNDO/2 MO calculation methods have been applied to $C_6H_5YCH_2Cl$(Y = None, -$CH_2$-, -O-, -S-, -CO-, -$SO_2$-). It has been shown that charge distributions in molecules are mainly controlled by the migration of valence inactive electron, giving the order of ${\sigma}$-acceptor and ${\pi}$-donor effects -O- > -S- > -$CH_2$- > -$SO_2$-. The -CO- group exceptionally acts as ${\sigma}$-donor and ${\pi}$-acceptor. It was also predicted that, $S_N2$ reactivities of C$C_6H_5YCH_2Cl$ would be in the order of -O-${\thickapprox}$-CO- >>-S-${\thickapprox}$None > -$CH_2$-, neglecting solvent effect. From the results of our studies, we conclude that the structural factors influencing 의 $S_N$ reactivities will be: (1) positive charge developments on reaction center carbon atom (2) energy level of ${\sigma}$-antibonding unoccupied MO with respect to C-Cl bond. (3) ${\sigma}$-antibonding strength of C-Cl bond at that level.



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