ISSN:
0009-2940
Keywords:
Bond activation
;
C—H
;
C—C
;
Iron chemistry
;
Reaction mechanisms
;
Chelate effects
;
Tandem mass spectrometry
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
For three α,ω-diphenylalkanes the mechanistic details of the Fe+-mediated activation of C—H and C—C bonds in the gas phase have been elucidated by isotopic labelling experiments. The unimolecular reactions, i.e. dehydrogenation of the alkane chain, formation of ethylene from internal methylene groups, and generation of toluene, proceed largely with high selectivity. Particularly interesting are the results for the dehydrogenation of the Fe+ complex 3-Fe+ of 1,8-diphenyloctane which involves to 93% the internal methylene groups C-4/C-5. In addition, the study of the stereoisotopomers 3c-d provides evidence for the operation of isotopically sensitive branching (“metabolic switching”) in the reaction, and the analysis of the data suggests that the selectivity of the reaction is, most likely, due to a sandwich-type structure.
Additional Material:
3 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19941270136
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