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

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

研究成果: ジャーナルへの寄稿記事

8 引用 (Scopus)

抄録

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.

元の言語英語
ページ(範囲)280-287
ページ数8
ジャーナルJournal of Organometallic Chemistry
611
発行部数1-2
DOI
出版物ステータス出版済み - 10 6 2000
外部発表Yes

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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

これを引用

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

:: Journal of Organometallic Chemistry, 巻 611, 番号 1-2, 06.10.2000, p. 280-287.

研究成果: ジャーナルへの寄稿記事

Kang, Song Yun ; Yoshizawa, Kazunari ; Yamabe, Tokio ; Naka, Akinobu ; Ishikawa, Mitsuo. / An ab initio study on the structure and reactivity of 1,4-disilabenzene. :: Journal of Organometallic Chemistry. 2000 ; 巻 611, 番号 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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