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

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6 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)520-529
Number of pages10
JournalBulletin of the Chemical Society of Japan
Volume83
Issue number5
DOIs
Publication statusPublished - 2010 May 21

ASJC Scopus subject areas

  • Chemistry(all)

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