An ab initio MO study structure and reactivity of 4-silatriafulvene

T. Veszprémi, Masae Takahashi, Jun Ogasawara, Kenkichi Sakamoto, Mitsuo Kira

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Abstract

The structures and reactions of 4-silatriafulvene were studied in detail by ab initio molecular orbital theory. At the equilibrium structure, 4-silatriafulvene shows severe bending about the Si=C double bond. A planar structure having two conjugated double bonds (an Si=C and a C=C double bond in the cyclopropenyl moiety) is the transition state for flopping between the two degenerate bent structures; the activation energy is within 1 kcal/mol at MP2/6-311++G** + ZPE. It is concluded that 4-silatriafulvene is balanced by two stabilizing factors, aromaticity of the cyclopropenyl moiety and Si=C double-bond formation. The remarkably low reactivity of a 4-silatriafulvene toward water that was found experimentally is reproduced theoretically by comparing the transition structures and activation energies with those of silaethene + water. Intramolecular isomerization from 4-silatriafulvene to silacyclobutadiene via cyclopropenylsilylene is even competitive with the water-addition reaction.

Original languageEnglish
Pages (from-to)2408-2414
Number of pages7
JournalJournal of the American Chemical Society
Volume120
Issue number10
DOIs
Publication statusPublished - Mar 18 1998

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Water
Activation energy
Addition reactions
Molecular orbitals
Isomerization

ASJC Scopus subject areas

  • Chemistry(all)

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An ab initio MO study structure and reactivity of 4-silatriafulvene. / Veszprémi, T.; Takahashi, Masae; Ogasawara, Jun; Sakamoto, Kenkichi; Kira, Mitsuo.

In: Journal of the American Chemical Society, Vol. 120, No. 10, 18.03.1998, p. 2408-2414.

Research output: Contribution to journalArticle

Veszprémi, T. ; Takahashi, Masae ; Ogasawara, Jun ; Sakamoto, Kenkichi ; Kira, Mitsuo. / An ab initio MO study structure and reactivity of 4-silatriafulvene. In: Journal of the American Chemical Society. 1998 ; Vol. 120, No. 10. pp. 2408-2414.
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abstract = "The structures and reactions of 4-silatriafulvene were studied in detail by ab initio molecular orbital theory. At the equilibrium structure, 4-silatriafulvene shows severe bending about the Si=C double bond. A planar structure having two conjugated double bonds (an Si=C and a C=C double bond in the cyclopropenyl moiety) is the transition state for flopping between the two degenerate bent structures; the activation energy is within 1 kcal/mol at MP2/6-311++G** + ZPE. It is concluded that 4-silatriafulvene is balanced by two stabilizing factors, aromaticity of the cyclopropenyl moiety and Si=C double-bond formation. The remarkably low reactivity of a 4-silatriafulvene toward water that was found experimentally is reproduced theoretically by comparing the transition structures and activation energies with those of silaethene + water. Intramolecular isomerization from 4-silatriafulvene to silacyclobutadiene via cyclopropenylsilylene is even competitive with the water-addition reaction.",
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AU - Kira, Mitsuo

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N2 - The structures and reactions of 4-silatriafulvene were studied in detail by ab initio molecular orbital theory. At the equilibrium structure, 4-silatriafulvene shows severe bending about the Si=C double bond. A planar structure having two conjugated double bonds (an Si=C and a C=C double bond in the cyclopropenyl moiety) is the transition state for flopping between the two degenerate bent structures; the activation energy is within 1 kcal/mol at MP2/6-311++G** + ZPE. It is concluded that 4-silatriafulvene is balanced by two stabilizing factors, aromaticity of the cyclopropenyl moiety and Si=C double-bond formation. The remarkably low reactivity of a 4-silatriafulvene toward water that was found experimentally is reproduced theoretically by comparing the transition structures and activation energies with those of silaethene + water. Intramolecular isomerization from 4-silatriafulvene to silacyclobutadiene via cyclopropenylsilylene is even competitive with the water-addition reaction.

AB - The structures and reactions of 4-silatriafulvene were studied in detail by ab initio molecular orbital theory. At the equilibrium structure, 4-silatriafulvene shows severe bending about the Si=C double bond. A planar structure having two conjugated double bonds (an Si=C and a C=C double bond in the cyclopropenyl moiety) is the transition state for flopping between the two degenerate bent structures; the activation energy is within 1 kcal/mol at MP2/6-311++G** + ZPE. It is concluded that 4-silatriafulvene is balanced by two stabilizing factors, aromaticity of the cyclopropenyl moiety and Si=C double-bond formation. The remarkably low reactivity of a 4-silatriafulvene toward water that was found experimentally is reproduced theoretically by comparing the transition structures and activation energies with those of silaethene + water. Intramolecular isomerization from 4-silatriafulvene to silacyclobutadiene via cyclopropenylsilylene is even competitive with the water-addition reaction.

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