Conformational behavior and electronic structure of silylketenes studied with quantum chemical calculations and photoelectron spectroscopy

Heidi M. Muchall, Nick H. Werstiuk, Jiangong Ma, Thomas T. Tidwell, Kuang-Sen Sung

Research output: Contribution to journalArticle

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Abstract

The He(I) photoelectron spectra of silylketenes (Me3Si)2C=C=O (1), Me5Si2CH=O=O (2), Me2Si(CH=O=O)2 (3), MeSi(CH=C=O)3 (4), (SiMe2CH=C=O)2 (5), and (CH2SiMe2CH=C=O)2 (6) have been recorded and their structures and orbital energies have been calculated by ab initio methods. Orbital energies for disilanes 2 and 5 are strongly dependent on a Si-Si-C-C torsional angle due to σ-π orbital interaction. Comparisons between experimental and simulated spectra show that 2 and 5 prefer conformations in which the Si-Si bond and ketene group(s) are approximately orthogonal (113° and 111°, respectively). Silylalkenes Me5Si2CH=CH2 (7) and (SiMe2CH=CH2)2 (8), which have been included in the computational study, show the same behavior as their corresponding silylketenes. Silylbis- and trisketenes 3-6 do not exhibit π-π interaction of any significance. For Si-Si containing compounds, the best agreement between experimental and computed data was obtained when Becke3LYP/6-31G*//HF/3-21G* was employed.

Original languageEnglish
Pages (from-to)1851-1861
Number of pages11
JournalCanadian Journal of Chemistry
Volume75
Issue number12
DOIs
Publication statusPublished - 1997 Jan 1

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Photoelectron spectroscopy
Photoelectrons
Electronic structure
Conformations
ketene

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

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title = "Conformational behavior and electronic structure of silylketenes studied with quantum chemical calculations and photoelectron spectroscopy",
abstract = "The He(I) photoelectron spectra of silylketenes (Me3Si)2C=C=O (1), Me5Si2CH=O=O (2), Me2Si(CH=O=O)2 (3), MeSi(CH=C=O)3 (4), (SiMe2CH=C=O)2 (5), and (CH2SiMe2CH=C=O)2 (6) have been recorded and their structures and orbital energies have been calculated by ab initio methods. Orbital energies for disilanes 2 and 5 are strongly dependent on a Si-Si-C-C torsional angle due to σ-π orbital interaction. Comparisons between experimental and simulated spectra show that 2 and 5 prefer conformations in which the Si-Si bond and ketene group(s) are approximately orthogonal (113° and 111°, respectively). Silylalkenes Me5Si2CH=CH2 (7) and (SiMe2CH=CH2)2 (8), which have been included in the computational study, show the same behavior as their corresponding silylketenes. Silylbis- and trisketenes 3-6 do not exhibit π-π interaction of any significance. For Si-Si containing compounds, the best agreement between experimental and computed data was obtained when Becke3LYP/6-31G*//HF/3-21G* was employed.",
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Conformational behavior and electronic structure of silylketenes studied with quantum chemical calculations and photoelectron spectroscopy. / Muchall, Heidi M.; Werstiuk, Nick H.; Ma, Jiangong; Tidwell, Thomas T.; Sung, Kuang-Sen.

In: Canadian Journal of Chemistry, Vol. 75, No. 12, 01.01.1997, p. 1851-1861.

Research output: Contribution to journalArticle

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T1 - Conformational behavior and electronic structure of silylketenes studied with quantum chemical calculations and photoelectron spectroscopy

AU - Muchall, Heidi M.

AU - Werstiuk, Nick H.

AU - Ma, Jiangong

AU - Tidwell, Thomas T.

AU - Sung, Kuang-Sen

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AB - The He(I) photoelectron spectra of silylketenes (Me3Si)2C=C=O (1), Me5Si2CH=O=O (2), Me2Si(CH=O=O)2 (3), MeSi(CH=C=O)3 (4), (SiMe2CH=C=O)2 (5), and (CH2SiMe2CH=C=O)2 (6) have been recorded and their structures and orbital energies have been calculated by ab initio methods. Orbital energies for disilanes 2 and 5 are strongly dependent on a Si-Si-C-C torsional angle due to σ-π orbital interaction. Comparisons between experimental and simulated spectra show that 2 and 5 prefer conformations in which the Si-Si bond and ketene group(s) are approximately orthogonal (113° and 111°, respectively). Silylalkenes Me5Si2CH=CH2 (7) and (SiMe2CH=CH2)2 (8), which have been included in the computational study, show the same behavior as their corresponding silylketenes. Silylbis- and trisketenes 3-6 do not exhibit π-π interaction of any significance. For Si-Si containing compounds, the best agreement between experimental and computed data was obtained when Becke3LYP/6-31G*//HF/3-21G* was employed.

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