An ab initio study on the structure and reactivity of 1,4-disilabenzene

Song Yun Kang, Kazunari Yoshizawa, Tokio Yamabe, Akinobu Naka, Mitsuo Ishikawa

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Abstract

Possible reaction pathways for the conversion of Dewar-type 1,4-disilabenzene (1) to 1,4-disilabenzene (2) are discussed by means of B3LYP/6-31G** density functional theory and multiconfigurational CASSCF(6,6)/6-31G** calculations. The activation energy for the symmetry-allowed conrotatory ring opening of 1 is 34.6 kcal mol-1 at the B3LYP level and 47.7 kcal mol-1 at the CASSCF level, and that for the symmetry-forbidden disrotatory ring opening is 36.6 kcal mol-1 and 54.3 kcal mol-1 at the same levels. In both calculations the conrotatory ring opening of 1 proceeds through a potential energy barrier that is 2.0-6.6 kcal mol-1 lower than that of the disrotatory ring opening. Thus, we conclude that the conrotatory pathway is energetically more preferred than the disrotatory pathway. The Diels-Alder reaction of 1,4-disilabenzene and acetylene is also discussed. The activation energy for the Diels-Alder addition is computed to be 4.2 kcal mol-1 at the B3LYP/6-31G** level. Thus, 1,4-disilabenzene is highly reactive, and once 1,4-disilabenzenes are produced, the Diels-Alder additions of 1,4-disilabenzenes with many kinds of dienophiles should readily take place.

Original languageEnglish
Pages (from-to)280-287
Number of pages8
JournalJournal of Organometallic Chemistry
Volume611
Issue number1-2
DOIs
Publication statusPublished - Oct 6 2000
Externally publishedYes

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Conversion Disorder
Acetylene
Cycloaddition Reaction
reactivity
Activation energy
Dewars
rings
Energy barriers
Potential energy
Density functional theory
activation energy
Diels-Alder reactions
symmetry
acetylene
potential energy
density functional theory

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

An ab initio study on the structure and reactivity of 1,4-disilabenzene. / Kang, Song Yun; Yoshizawa, Kazunari; Yamabe, Tokio; Naka, Akinobu; Ishikawa, Mitsuo.

In: Journal of Organometallic Chemistry, Vol. 611, No. 1-2, 06.10.2000, p. 280-287.

Research output: Contribution to journalArticle

Kang, Song Yun ; Yoshizawa, Kazunari ; Yamabe, Tokio ; Naka, Akinobu ; Ishikawa, Mitsuo. / An ab initio study on the structure and reactivity of 1,4-disilabenzene. In: Journal of Organometallic Chemistry. 2000 ; Vol. 611, No. 1-2. pp. 280-287.
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abstract = "Possible reaction pathways for the conversion of Dewar-type 1,4-disilabenzene (1) to 1,4-disilabenzene (2) are discussed by means of B3LYP/6-31G** density functional theory and multiconfigurational CASSCF(6,6)/6-31G** calculations. The activation energy for the symmetry-allowed conrotatory ring opening of 1 is 34.6 kcal mol-1 at the B3LYP level and 47.7 kcal mol-1 at the CASSCF level, and that for the symmetry-forbidden disrotatory ring opening is 36.6 kcal mol-1 and 54.3 kcal mol-1 at the same levels. In both calculations the conrotatory ring opening of 1 proceeds through a potential energy barrier that is 2.0-6.6 kcal mol-1 lower than that of the disrotatory ring opening. Thus, we conclude that the conrotatory pathway is energetically more preferred than the disrotatory pathway. The Diels-Alder reaction of 1,4-disilabenzene and acetylene is also discussed. The activation energy for the Diels-Alder addition is computed to be 4.2 kcal mol-1 at the B3LYP/6-31G** level. Thus, 1,4-disilabenzene is highly reactive, and once 1,4-disilabenzenes are produced, the Diels-Alder additions of 1,4-disilabenzenes with many kinds of dienophiles should readily take place.",
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