Abstract
Mono- and bis(trifluoromethylthio)-substituted and perfluorooctanesulfonylferrocene
derivatives were prepared by nucleophilic substitution reactions
on the ferrocene core. Thus, Hg(SCF3 )2 was
activated in situ by Cu and used for nucleophilic displacement reactions
of bromide. Trifluoromethylsulfonylferrocene was not accessible
by this method. The reaction of lithioferrocene with trifluoromethylsulfonyl
chloride gave chloroferrocene in small yield, presumably due to
the high lattice energy of solid LiF. On the other hand, the known
trifluoromethylferrocene was obtained as the only isolable compound
from the photochemical reaction of CF3 SSCF3 with
ferrocene. The same product was detected in small amounts in the
reaction of chloromercuryferrocene with trifluoromethylsulfonyl
chloride. It thus appears that most established methods for trifluoromethylation
of purely organic compounds fail for ferrocene due to concurring
redox reactions. The new compounds have been comprehensively characterized
by elemental analyses, NMR and IR spectroscopy, mass spectrometry,
and electrochemistry. The SCF3 group appears to be almost
as electron-withdrawing as a trifluoromethyl group on the ferrocene
core.
Key words
electrochemistry - ferrocene - fluoro compounds - trifluoromethyl
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