PMO Theory of Orbital Interaction (Part 6). Sigma-Aromatic Orbital Interactions in Heteroatom Analogues of Trimethylene Diradical

궤도간 상호작용의 PMO 이론 (제6보). 트리메틸렌 디라디칼의 헤테로 원자 유사체내에서의 시그마 방향족성 궤도간 상호작용

  • Lee Ik Choon (Department of Chemistry, Inha University) ;
  • Kim Ho Soon (Department of Chemistry, Inha University) ;
  • Choi Jae Ho (Department of Chemistry, Inha University)
  • 이익춘 (인하대학교 이과대학 화학과) ;
  • 김호순 (인하대학교 이과대학 화학과) ;
  • 최재호 (인하대학교 이과대학 화학과)
  • Published : 1985.04.20


Orbital interactions between two nonbonding orbitals have been investigated for heteroatom analogues of trimethylene diradical using MINDO/3 and STO-3G methods. The results showed that the conformers in which significant ${\sigma}$-aromatic stabilization is involved exhibited level order reversal to $n_-$ below $n_+$ as it was found for trimethylene diradical. Lone pair orbitals (LPO) were found to be stabilized by charge dispersion accompanying vicinal trans $n-{\sigma}^*$ interaction and hydrogen bonding. In systems with different heteroatoms, N and O, the contribution of the LPO of oxygen, $n_O$ was always greater in the lower level whereas that of nitrogen, nN, was greater in the higher level as can be expressed as : $n_{\pm}$(lower) = $n_O{\pm}{\lambda}_Nn_N.\;n_{\pm}(higher)\;=\;n_N{\pm}{\lambda}_On_O$. where ${\lambda}_i$< 1.0



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