ISSN:
0018-019X
Keywords:
Chemistry
;
Organic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Fourier-transform ion-cyclotron-resonance (FTICR) mass spectrometry has been used to uncover the mechanisms by which FeO+ dehydrates heptan-4-one (5a) and nonan-5-one (6a) in the gas phase. The study of isotopomeric ketones provides evidence that H2O loss is not due to a 1,1-elimination, thus ruling out the intermediacy of high-valent iron-carbene species. Rather, H2O is generated in a formal 1,2-elimination involving the ω/ω - 1 positions of the alkyl chain (‘remote C—H bond activation’). In the consecutive alkene/H2O elimination, the olefins (ethylene from 5a and propene from 6a) originate from the terminal part of one alkyl chain, and the H-atom is transferred to the FeO+ moiety in the course of this process, builds up together with an H-atom from the ω/ω-1 position of the other alkyl chain the H2O molecule. In either case, the O-atom of H2O is provided by the FeO+ species.
Additional Material:
1 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/hlca.19900730217
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