ISSN:
0009-2940
Keywords:
Nitronium ions
;
One-electron oxidation
;
Superacidic systems
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
(F3CS)3N (1) is oxidized quantitatively by AsF5 to the first bis(perfluoroalkylthio)nitronium salt (F3CS)2N+AsF-6 (2). Addition of halide ions (F-, Cl-, Br-, l-) to the cation of 2 destroys the S—N—S chain. (F2CSCl)2 undergoes with ammonia a cyclization reaction to S—CF2—CF2—S—N—H (3), which can be derivatized with F3CSCl or (F2CSCl)2 to S—CF2—CF2—S—N—SCF3 (3a) and (S—CF2—CF2—S—N—SCF2—)2 (3b), respectively. Oxidation of 3a with AsF5 yields (S—CF2—CF2—S—N+AsF-6 (4) and byproducts, which suggest formation of a {3a}+• radical cation as an intermediate in this reaction. Pure 4 is accessible by reaction of 3 with AsF5 in 54% yield. The chemical and spectroscopic properties of the new species are discussed.
Additional Material:
1 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19951280416
