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Physical Data: mp 173-174 °C; sublimes slowly at room temperature, rapidly at 100 °C; bp 249 °C; d 1.49 g cm-3.
Solubility: sol all common organic solvents; insol water.
Form Supplied in: deep orange crystals; widely available.
Handling, Storage, and Precautions: stable up to 470 °C; stable to alkalis and, in the absence of air, to strong, non-oxidizing acids; oxidized by air in the presence of strong acids and by many oxidizing agents, including HNO3 and the halogens, reversibly forming the cation (C5H5)2Fe+.
Ferrocene1,2 is a typically aromatic system and as such has a wide-ranging chemistry based on its substitution reactions. As a synthetic reagent its primary use is as a source of useful ferrocene derivatives themselves. These include sensors, which make use of the readily reversible oxidation of ferrocene and its derivatives, monomers for the synthesis of redox active polymers, compounds with nonlinear optical properties, and antianaemic agents. Ferrocene also serves as the source of cationic complexes of benzene derivatives, which are thereby rendered reactive towards nucleophiles. Although ferrocene derivatives can be cleaved to yield cyclopentane or cyclopentadiene derivatives, it has only rarely found use for this purpose.
With only the limits imposed by their facile oxidation, ferrocene derivatives undergo all the common functional group transformations of arenes. It is appropriate here to review only the principal direct substitution processes with emphasis on differences from the chemistry of benzenoid aromatics. These arise chiefly from the impossibility of effecting direct halogenation or nitration since all potential reagents oxidize ferrocene to the unreactive ferrocenium cation [Fe(C5H5)2]+. This cation itself is a very mild one-electron oxidizing agent which has frequently been employed to oxidize other organometallic species.
The ferrocenyl group, C5H5FeC5H4, is commonly abbreviated as Fc.
Friedel-Crafts acylation [with acid chlorides/AlCl3 (eq 3) or acid anhydrides/BF3] is readily regulated by the choice of reaction conditions to give mono- or disubstitution; the latter includes a very small amount of 1,2-disubstitution.1 Column chromatography readily separates mixtures. Sulfonation, best done with Chlorosulfonic Acid,7 is more difficult to regulate (eq 4).
The boronic acid is an alternative precursor of haloferrocenes and can similarly give acetoxyferrocene, both by reaction with copper salts (eq 10).17 The acetate reacts with Grignard reagents to give hydroxyferrocene, but both this phenolic compound and aminoferrocene are very sensitive to oxidation and relatively little is known of their chemistry.
Formation and Uses of (Arene)cyclopentadienyliron Cations.
The cyclohexadienyl groups can generally be rearomatized by reaction with N-Bromosuccinimide (eq 16)24 or in some cases trityl salts,24b thus opening the way to further additions, but cyano, benzyl, malonyl, and similarly reactive exo substituents are cleaved by these reagents.
Ferrocene resists hydrogenation under conditions which readily convert benzene to cyclohexane and has only been reduced (to metal and cyclopentane) at ca. 350 °C using a Raney Nickel catalyst.36a It is cleaved by an excess of Bromine to give pentabromocyclopentane;36 neither of these degradations has been applied to derivatives.
In an attempt to extend the latter example to tricyclic systems, appropriately substituted (amidophenyl)ferrocenes were prepared as precursors via arylation (eq 5) of ferrocene with 2-nitro- and with 2-cyanobenzenediazonium salts. The final Bischler-Napieralski type cyclization step appeared to proceed smoothly, but instead of the expected fused ferrocenes (isolated in low yield when n = 1) the metal-free heterocycles were the main products (eq 27);42 i.e. cleavage had occured without quaternization even in the dark.
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