Ferrocene Synthesis

Iminophosphoranes, mercuration, 2, 432 (Iminophosphoranyl)ferrocenes, synthesis, 6, 202 Imino-pyrrolate systems, with zirconium, 4, 1138-1139 Imino-pyrrolides, with Zr(IV) and Hf(IV), 4, 780 Imino-pyrrolyl ligands, in chromium complexes, 5, 355 Iminosilanes, reactions, 3, 440 Imprinted complexes, on oxide surface, 12, 810 Impurities, glovebox techniques, 1, 215 Inclusion chemistry... 

Ferrocene is prepared in 40-50% conversion by the reaction of activated iron obtained by the reaction of iron oxide with hydrogen, with cyclopentadiene as shown in eq. (15.2) by Miller, Tebboth and Tremaine [8] in 1952. Ferrocene synthesis by this direct reaction process, was published later than the reaction with... 

Barley HRL, Clegg W, Dale SH et al (2005) Alkali-metal-mediated zincation of ferrocene synthesis, structure, and reactivity of a lithium-TMP-zincate reagent. Angew Chem Int Ed 44 6018-6021. doi 10.1002/anie.200501560... 

Phosphine-Containing Planar Chiral Ferrocenes Synthesis, Coordination Chemistry and Applications to Asymmetric Catalysis... 

Properties of ferrocene-containing polymers have been improved by inclusion of pyrazole systems in the backbone. The synthesis of (748) was achieved by condensation of bis()3-diketoferrocenes) with aromatic dihydrazines to give polyhydrazones that were later cyclo-dehydrated (B-80MI40408). 

Cyclopentadiene, b.p. 40°, is obtained by heating commercial 85% dicyclopentadiene (e.g., from Matheson, Coleman and Bell Company, Norwood, Ohio) under a short column (M in. diameter X 8-12 in. length) filled with glass helices. The distilled cyclopentadiene is collected in a receiver which is maintained at Dry Ice temperature until the cyclopentadiene is used. Methylcyclopentadiene and other substituted cyclopentadienes such as indene may also be employed for the synthesis of the correspondingly substituted ferrocenes. In these cases, the reaction of the hydrocarbon with sodium is much slower than with cyclopentadiene, and refluxing for several hours is required to complete the reaction. 

Other interesting synthetic applications of the ketone-derived enamine alkylation are found in the monomethylation of steroid enamines (249), extension of the benzylation reaction (250) to a ferrocene derivative (251), the use of a-bromoesters (252) and ketones (252) or their vinylogues (25J), in the syntheses of alantolactone (254-256), isoalantolactone (257), and with a bridged bis-enamine (258). The use of bifunctional alkylating agents is also seen in the introduction of an acetylenic substituent in the synthesis of the characteristic fragrant constituent of jasmine (259), the synthesis of macrocyclic ketolactones (260), the use of butyrolactone (261), and the intermolecular or intramolecular double alkylations of enamines with dihalides (262). 

The synthesis of cyclopentadienyliron(Ti -indolyl) proceeds through formation of 110 (88PAC1193). Transformation into the -complex occurs at elevated temperatures. Carbazole forms only the A-carbazolyl complex 111 under these circumstances. However, carbazole with ferrocene and aluminum chloride/aluminum powder gives the Ti -coordinated dication 112 [80JOM(186)265]. 

The synthesis, chemical properties, and structural analysis of l,T-diphospha-ferrocene have been described [78JOM(156)C33 80AX(B)1344 80JA994 ... 

With OH and SH, the nucleophilic substitution of Cl has been reported. Thus, with NaOH, there is a report of successful nucleophilic substitution in 50% aq. acetone at room temperature to give the phenol complex in 36% yield. The latter is then spontaneously deprotonated to give the cyclohexadienyl complex (Eq. (24)). An identical reaction was carried out using NaSH in MeCN (50% yield) to give the thiophenol complex which was deprotonated [72] Eq. (25). These reactions would be especially valuable because direct synthesis of the phenol or thiophenol complexes from ferrocene is not possible due to the strong interaction between the heteroatom and A1C13 [11, 19]. Recent improvement and use of this reaction were achieved [88],... 

Poly(arylene thioether)s, 363-364 Poly(arylene thioether sulfone)s, 364 Poly(aryl sulfone) derivatives, 354 Poly(p-benzamide), synthesis of, 188-189 Polybenzimidazoles (PBIs), 265 ferrocene-containing, 315 synthesis of, 313... 

The original synthesis of metallacarborancs is effected by deprotonation of nido-carborane anions in a manner like that employed to prepare ferrocene, e.g. ... 

The synthesis of the unsymmetrical imidazolium salt 11 bearing a planar-chiral ferrocene was described by Bolm starting from (Rp)-[2-(trimethysilyl)-ferrocenyl] methanol 12 which afforded the salt in good yield after reaction with Ar,M-carbonyl diimidazole and methylation (Scheme 9) [18]. 

Fig. 27 Synthesis of pentaphenyl ferrocene oxazoline palladacycle precatalyst 53-Cl...

In 1996, Fu et al. reported the S3mthesis of the planar chiral heterocycles 64, formally DMAP fused with a ferrocene core [82]. While the original synthesis provided racemic 64a in only 2% overall yield requiring a subsequent resolution by preparative HPLC on a chiral stationary phase, a recently improved synthesis furnished the racemic complexes 64 in 32-40% yield over seven steps. A subsequent resolution with di-p-toluoyltartaric or dibenzoyltartaric acid gave access to the enantiomers with >99% ee (28 14% yield for each isomer in this step) [83]. 

Crespo, O., Canales, F., Gimeno, M.C., Jones, P.G. and Laguna, A. (1999) Synthesis of [Au2(SC6F5)2( l-dppf)] and [Au2(p-SC6F5)(p-dppf)j (dppf = l,l -Bis (diphenylphosphino)ferrocene). Reactivity toward Various Metallic Fragments. Organometallics, 18(16), 3142-3148. 

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