Xb. Ou et Af. Janzen, OXIDATIVE FLUORINATION IN THE PH(2)SO-XEF2-CL- SYSTEM AND FLUORINE EXCHANGE IN THE PH(2)S(O)F-2-PH(2)S(O)F+ SYSTEM, Canadian journal of chemistry, 74(11), 1996, pp. 2002-2007
Oxidative fluorination of diphenyl sulfoxide with xenon difluoride occ
urs under mild conditions in the presence of chloride ion to give Ph(2
)S(O)F-2 in quantitative yield. Chloride ion appears to react with xen
on difluoride to generate fluoride ion, and a mechanism of oxidative f
luorination is proposed that involves anionic Ph(2)S(OF- and radical P
h(2)S(O)F-. intermediates. Addition of cationic Ph(2)S(OF+ to Ph(2)S(O
)F-2 initiates rapid fluorine exchange, presumably via a symmetrical f
luorine-bridged intermediate, and this exchange process was monitored
by C-13 and F-19 NMR spectroscopy. In the presence oi chloride ion, Ph
(2)S(O)Cl-2 is formed and can be identified by C-13 NMR and by its hyd
rolysis to Ph(2)SO(2). Mechanisms are proposed for these reactions, an
d ab initio molecular orbital calculations (GAUSSIAN92) were carried o
ut of the postulated intermediates.