Acetylketene: Conformational isomerism and photochemistry. Matrix isolation infrared and ab initio studies

Kappe C.O., Wong M.W. and Wentrup C. (1995) Acetylketene: Conformational isomerism and photochemistry. Matrix isolation infrared and ab initio studies. Journal of Organic Chemistry, 60 6: 1686-1695.

Author Kappe C.O.
Wong M.W.
Wentrup C.
Title Acetylketene: Conformational isomerism and photochemistry. Matrix isolation infrared and ab initio studies
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
Publication date 1995-01-01
Sub-type Article (original research)
Volume 60
Issue 6
Start page 1686
End page 1695
Total pages 10
Subject 1605 Policy and Administration
Abstract The s-Z and s-E conformers of acetylketene (5) were generated by flash vacuum pyrolysis (FVP) and matrix photolysis of precursors 1-4. Both conformers were characterized by low-temperature IR spectroscopy in argon, xenon, and nitrogen matrices. The observed frequencies and intensities are in excellent agrement with ab initio calculations at the MP2/6-31G* level. UV irradiation of s-Z/s-E-5 in nitrogen or xenon matrices allows the clean interconversion of conformers. Prolonged UV irradiation resulted in decarbonylation and formation of methylketene (7). However, the photolysis of argon matrix isolated 5 produced a new set of bands in the IR spectrum very close to the s-Z/s-E absorptions. Annealing of the matrix to 35 K removed these bands. This unusual phenomenon was shown to be due to a photochemically induced matrix site effect. Consistent with experimental observations, high-level calculations (QCISD(T)/6-311+G(2d,p)+ZPVE) predict that the s-Z and s-E conformers have virtually identical energies.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: Scopus Import
 
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