Substituent effects on inversion motion of 4-silatriafulvene derivatives: An Ab initio MO study

Masae Takahashi, Kenkichi Sakamoto, Mitsuo Kira

研究成果: Conference article査読

17 被引用数 (Scopus)

抄録

The structure and spectroscopic characteristics of various 4-silamethylenecyclopropene (4-silatriafulvene) derivatives were investigated using ab initio MO calculations. The minimum energy geometries of all of the derivatives studied here were trans-bent around the Si=C double bond, and the planar structures were found to be the transition states for the inversion motion between the two equivalent bent structures. The barriers were very low to allow facile inversion at room temperature. It was found that silyl substitution at the unsaturated silicon lowered the barrier height of the inversion motion. Significant differences were found in the calculated absorption maxima and 29Si NMR chemical shifts between the planar and trans-bent 4-silatriafulvene derivatives, which suggested significant temperature dependence in the spectra. All of these features were in good agreement with the experimental results for a 4-silatriafulvene derivative, 1,2-di-tert-butyl-4,4-bis(tert-butyldimethylsilyl)-4-silamethylenecyclopropene, that we recently isolated.

本文言語English
ページ(範囲)198-207
ページ数10
ジャーナルInternational Journal of Quantum Chemistry
84
2
DOI
出版ステータスPublished - 2001 8 5
外部発表はい
イベント3th European Conference on Computational Chemistry (EUCO-CC3) - Budapest, Hungary
継続期間: 2000 9 42000 9 8

ASJC Scopus subject areas

  • 原子分子物理学および光学
  • 凝縮系物理学
  • 物理化学および理論化学

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