Theoretical Study of Bond-Switching in 1,6-Dihydro-6athia-1,6- diazapentalene (10-S-3) Systems Compared with Corresponding Oxygen Analogues

Teruo Atsumi, Tomohiro Abe, Kin Ya Akiba, Hiromi Nakai

研究成果: Article査読

6 被引用数 (Scopus)

抄録

Theoretical study of the mechanism of bond-switching of 5-(1-aminoethylimino)-3-methyl-1,2,4-thiadiazole and 5-(2-aminovinyl)isothiazole was carried out by using simplified models of 1,6-dihydro-6a-thia-1,6- diazapentalene (10-S-3) systems and corresponding oxygen analogs. Geometries and energetics were examined along unimolecular and bimolecular reaction paths by hybrid density functional theory (DFT) calculations with triple-zeta class basis sets by taking into account solvent effects which is estimated by the polarizable continuum model. It was clarified that the unimolecular reactions cannot proceed due to the high energy barriers around 70 kcalmol-1. On the other hand, the bimolecular processes in neutral and acidic conditions can be accomplished for the sulfur compounds, not for the oxygen ones. The differences of the reactivities between the sulfur and oxygen compounds were found to be due to the difference of the stability of the symmetric intermediates with the hypervalent three-center four-electron bonds.

本文言語English
ページ(範囲)520-529
ページ数10
ジャーナルBulletin of the Chemical Society of Japan
83
5
DOI
出版ステータスPublished - 2010

ASJC Scopus subject areas

  • Chemistry(all)

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