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Formation Mechanism of NF 4 + Salts and Extraordinary Enhancement of the Oxidizing Power of Fluorine by Strong Lewis Acids
Author(s) -
Christe Karl O.,
Haiges Ralf,
Vasiliu Monica,
Dixon David A.
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201701784
Subject(s) - oxidizing agent , chemistry , lewis acids and bases , radical , fluorine , reaction mechanism , thermal stability , inorganic chemistry , photochemistry , organic chemistry , catalysis
Although the existence of the NF 4 + cation has been known for 51 years, and its formation mechanism from NF 3 , F 2 , and a strong Lewis acid in the presence of an activation energy source had been studied extensively, the mechanism had not been established. Experimental evidence had shown that the first step involves the generation of F atoms from F 2 , and also that the NF 3 + cation is a key intermediate. However, it was not possible to establish whether the second step involved the reaction of a F atom with either NF 3 or the Lewis acid (LA). To distinguish between these two alternatives, a computational study of the NF 4 , SbF 6 , AsF 6 , and BF 4 radicals was carried out. Whereas the heats of reaction are small and similar for the NF 4 and LAF radicals, at the reaction temperatures, only the LAF radicals possess sufficient thermal stability to be viable species. Most importantly, the ability of the LAF radicals to oxidize NF 3 to NF 3 + demonstrates that they are extraordinary oxidizers. This extraordinary enhancement of the oxidizing power of fluorine with strong Lewis acids had previously not been fully recognized.