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

Title:

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

Muchall, Heidi M. and Werstiuk, Nick H and Ma, Jiagong and Tidwell, Thomas T. and Sung, Kuangsen (1997) Conformational behavior and electronic structure of silylketenes studied with quantum chemical calculations and photoelectron spectroscopy. Canadian Journal of Chemistry, 75 (12). pp. 1851-1861. ISSN 0008-4042

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Official URL: http://dx.doi.org/10.1139/v97-618

Abstract

The He(I) photoelectron spectra of silylketenes (Me3Si)2C=C=O (1), Me5Si2CH=C=O (2), Me2Si(CH=C=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.

Divisions:Concordia University > Faculty of Arts and Science > Chemistry and Biochemistry
Item Type:Article
Refereed:Yes
Authors:Muchall, Heidi M. and Werstiuk, Nick H and Ma, Jiagong and Tidwell, Thomas T. and Sung, Kuangsen
Journal or Publication:Canadian Journal of Chemistry
Date:December 1997
Funders:
  • Natural Sciences and Engineering Research Council of Canada
Keywords:conformational behavior, electronic structure, photoelectron spectroscopy, quantum chemical calculations, silylketenes
ID Code:6772
Deposited By:DANIELLE DENNIE
Deposited On:13 Jul 2010 11:08
Last Modified:08 Dec 2010 10:52
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