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Synthesis 2009(12): 2015-2018  
DOI: 10.1055/s-0029-1216812
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Perfluoroalkylthio-Substituted Ferrocenes

Constantin Rhode, Jessica Lemke, Max Lieb, Nils Metzler-Nolte*
Chair of Inorganic Chemistry I - Bioinorganic Chemistry, Faculty of Chemistry and Biochemistry, Ruhr-University Bochum, Universitätsstr. 150, 44801 Bochum, Germany
Fax: +49(234)3214378; e-Mail: nils.metzler-nolte@rub.de;
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Publikationsverlauf

Received 9 December 2008
Publikationsdatum:
27. Mai 2009 (online)

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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 CF3SSCF3 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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Lieb, M.; Metzler-Nolte, N. unpublished results.