ISSN:
1434-1948
Keywords:
Photolysis
;
Alkynes
;
Matrix isolation
;
DFT
;
Oxygenations
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Photolytically-induced reactions of chromyl chloride with acetylene and but-2-yne (dimethylacetylene) in low-temperature argon matrices yield end-on ketene and dimethylketene complexes of O=CrCl2, respectively. The product formation probably results from an electrophilic attack of a Cr=O linkage on the C≡C triple bonds, leading to radical-like transition states or intermediates, which subsequently rearrange through 1,2-H or 1,2-methyl shifts. Consequently, allene is attacked at its central carbon and the allyl radical thus generated undergoes subsequent ring-closure to give a cyclopropanone complex of O=CrCl2.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
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