- A matrix isolation study of the photochemically induced reactions of nitrogen dioxide with 1,2-dibromoethene and 1,2-dichloroethene using Fourier transform infrared spectroscopy
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Photolyses of matrices of either BrCHCHBr/NO2/Ar or ClCHCHCl/NO2/Ar using quartz-filtered radiation (λ > 240 nm) led to the appearance of infrared bands attributable to carbonyl, carbon monoxide, and ketene species; no bands belonging to a precursor complex NO 2...XCHCHX (where X = Br or Cl) were observed upon matrix deposition. The possible reaction pathway is discussed.
- Clark, Robin J.H.,Foley, Loraine J.
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p. 1389 - 1393
(2007/10/03)
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- HEI PHOTOELECTRON SPECTRA OF UNSTABLE MOLECULES: MONO- AND DIHALOGENOKETENES
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HeI Photoelectron spectra are reported for the mono- and di-chloro-and-bromo-ketenes (XHC=C=O and X2C=C=O, X=Cl,Br) generated in high yield as unstable molecules from thermolysis of acid halides.The spectra are discussed and assigned by reference to the parent ketene molecule, orbital trends, and comparison with theoretical calculations.
- Colbourne, David,Westwood, Nicholas P. C.
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p. 2049 - 2054
(2007/10/02)
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- Gasphasen-Reaktionen, 21. Thermische Erzeugung von Alkyl- und Halogenketenen
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Thermal gas phase reactions for the generation of ketenes can be optimized PE-spectroscopically.To eliminate HX from acetyl derivatives R2CH-COX increasing temperatures are required in the sequence HO2CCH3 ca.HCl HBr H2O ca.ROH CH4.By adding NH3, HCl can be removed from the gaseous mixture and thus the PE spectra of pure alkyl ketenes R2C=C=O (R e.g.H, CH3, C2H5) may be recorded. "Fulvene ketene" (4) is obtained from cyclopentadienecarbonyl chloride (this from the dimer) and ethyleneketene (7) by pyrolysis of cyclopropyl spirosubstituted Meldrum's acid (6).Chloro- and bromoketenes are generated as follows: ClHC=C=O from ClH2C-COCl, Cl2C=C=O from Cl3C-COBr with Zn, BrHC=C=O from 2-bromocyclobutanone and NC-HC=C=O from NC-HC=C=O from NC-H2C-COCl.The PE spectra are assigned by radical cation state comparison based on MNDO calculations.
- Bock, Hans,Hirabayashi, Takakuni,Mohmand, Shamsher
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p. 2595 - 2608
(2007/10/02)
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