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MO Theoretical Studies on the Effect of Bond Angle Distortion in Pyrazine
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  • MO Theoretical Studies on the Effect of Bond Angle Distortion in Pyrazine
  • MO Theoretical Studies on the Effect of Bond Angle Distortion in Pyrazine
저자명
Lee. Ik-Choon,Kim. Ho-Soon
간행물명
Bulletin of the Korean Chemical Society
권/호정보
1984년|5권 2호|pp.68-73 (6 pages)
발행정보
대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
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기타언어초록

An enhancement of through-bond interaction by bond angle distortion in pyrazine was examined using various MO methods. Results of MINDO/3 geometry optimization with an angle (${alpha}$) at $C_2$ atom fixed to 120∼90$^{circ}$ lead to distorted structures in which the distorted bond is brought closer toward lone pair orbital n of N atom. It was also found that the bond angle distortion increased the P character at the atom $C_2$, resulting in an increased vicinal overlap between n and the $C_2-C_3$ bond. The FMO patterns of ${sigma}$ framework showed three-fold degeneracy, one of which was of different symmetry which mixes in the symmetry adapted pair, $n_+;and;n_-;;both;n_+;and;n_-$ orbitals thus can interact with both FMOs of the ${sigma}$ framework. The LCBO-MO analysis with partial elimination of bonds, antibonds or both, however, revealed that the main interaction of $n_+$ was with the HO-${sigma}$ and that of $n_-$ was with the LU-${sigma}^{ast}$ orbital of the ${sigma}$ framework.