Ferrocene, Bis cyclopentadienyl iron

Formula (C5H5)2Fe or (ri-C5H5)2Fe MW 186.04 a metal n sandwich complex in which the six n electron system of the cyclopentadienidide ion CsHf is bound to Fe2+ ion Fe—C distance 2.045 A and C—C bond distance 1.4 A. Synonyms bis(cyclopentadienyl)iron ferrocene dicyclopentadienyliron... 

Synonyms/Trade Names bis(Cyclopentadienyl)iron, Ferrocene, Iron dicyclopentadienyl... 

The discovery in 1951 of the transition metal rr-complex, ferrocene or bis-cyclopentadienyl-iron, Fe(Cp)2, (1, 2) led to enormous interest being shown in the possible structures of such compounds and in the nature of the metal-ring bonding. Within a year the sandwich type structure (Fig. 1) had been proposed (2), and an outline treatment of the metal 3d-ligand 7r-orbital interaction by Jaffe (4) was soon followed by a more detailed molecular... 

Another example of a complex that obeys the 18-electron rule is ferrocene or bis(cyclopentadienyl) iron. The cyclopentadienyl anion is generated by the reaction of cydopentadiene with sodium, and ferrocene is obtained by the subsequent reaction with ferrous chloride,... 

The original concepts of metal-ligand bonding were essentially related to the dative covalent bond the development of organometallic chemistry has revealed a further way in which ligands can supply more than one electron pair to a central atom. This is exemplified by the classical cases of bis(benzene)chromium and bis(cyclopentadienyl)iron, trivial name ferrocene. These molecules are characterised by the bonding of a formally unsaturated system (in the organic chemistry sense, but expanded to include aromatic systems) to a central atom, usually a metal atom. 

Both in acetonitrile and in other non-aqueous solvents, a major problem arises in terms of the manner in which the potential values are reported by various investigators. Koepp, Wendt, and Strehlow [6] noted that hydrogen ion is the poorest reference material on which to base nonaqueous potentials because of the extreme differences in its solvation in various solvents. On the basis of an investigation of the solvent dependence of 18 redox couples, these investigators concluded that ferrocene/ferrocenium ion (i.e. bis(cyclopentadienyl)iron(III/II), abbreviated as Fc+ /Fc°) and/or cobal-tocene/cobalticenium ion represented optimal potential reference materials for nonaqueous studies. On the basis of their minimal charge (+1, 0) and their symmetry (treated as though they were roughly spherical), the potentials of these two redox couples are presumed to be relatively independent of solvent properties. 

The classic (if not classical) metal sandwich species bis(cyclopentadienyl)iron has the formula [(CH)5]2Fe (CpaFe) and the semisystematic name ferrocene, and so the related magnesium-containing species [(CHfsJaMg (CpaMg) is often accompanied by the name magnesocene. We commence our discussion with this species. 

The behavior of ferrocene, bis(cyclopentadienyl)iron(II), as an aromatic molecule under conditions for electrophilic substitution has received much attention by both organic and inorganic chemists (59, 63). The Friedel-Crafts acylation may illustrate the reactivity of this very stable compound. 

Bis( -cyclopentadienyl)iron 1, called ferrocene to emphasize the benzene-analogous reactivity (e. g., electrophilic alkylation and acylation), is not only the pioneer compound of organometallic chemistry [3-5]. It is also a platform for a plethora of derivatives and an efficient fuel additive, predominantly used in diesel fuels. This commercial use is based on the property that ferrocene undergoes homolytic decomposition under the conditions of fuel combustion. Ferrocene lowers the formation of soot particles upon combustion of diesel and ordinary fuel. 

Bis(cyclopentadienyl)iron derivatives, ferrocenes, are remarkably stable against heat and air and undergo various kinds of chemical reactions. They are usually prepared by the reaction of FeCh with an alkali metal salt of cyclopentadienyl or cyclopentadiene in the presence of base [51]. Although ferrocene derivatives basically have chemical reactivities similar to those of aromatic compounds, they have found only limited applications to organic synthesis so far. However, because chiral ferrocenylphosphines are capable of having both planar chirality and an asymmetry in the side chain in their rigid framework, they have been used recently in a number of asymmetric reactions. In this section, synthesis and developments of monocyclopentadienyl complexes and ferrocenylphosphines are described. The general chemistry of ferrocenes and half metallocene complexes is reviewed elsewhere [52-53]. 

A very successful mediator-chemically modified electrode (MCME) has been developed by using ferrocene derivatives (Cass et al., 1984). Ferrocene (bis-cyclopentadienyl iron) and its derivatives (FecpR) combine the good electrochemical behaviour of ferrocyanide with the possi-... 

Bis(cyclopentadienyl)iron or ferrocene is one of the most common organometallic subunits. Its use in supramolecular chemistry has been quite extensive during the last decade primarily for the following reasons ... 

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