Metalation, of ferrocene

A variety of alkali metal and metallocene-containing magnesium amides are known. Thus, attempted metallation of ferrocene using potassium tris(amido)magnesiate KMg N-(SiMe3)2 3 unexpectedly led to n-coordination of neutral ferrocene moieties to a pota-... 

Price, D. Simpkins, N. S. Concerning the asymmetric metalation of ferrocenes by chiral lithium amide bases. Tetrahedron Lett. 1995,... 

The metallation of ferrocene, for example lithiation and mercuration, has been the historically important route to the halogenated derivatives, Fc-X and fcX2-Scheme 5-3 summarizes the basic compounds that are useful intermediates for the synthesis of many ferrocenes bearing heteroatoms. 

Monoferrocenyllithium was prepared by direct metallation of ferrocene with t-BuLi, a procedure that resulted in the formation of traces of l,l -dilithio-ferrocene, explaining the obtention of the interesting diphosphine borane 40 in 3% yield. This has been exploited to prepare bidentate ligands, as detailed below. Other groups prepared other ferrocenyl monophosphines as can be... 

The first l,l -biferrocenyls containing P-stereogenic units were also reported by van Leeuwen and co-workers using a diastereoselective ort/zo-metallation of ferrocene ring as the key step (Scheme 4.23). 

Dayaker G, Sreeshailam A, Chevallier F et al (2010) Deprotonative metallation of ferrocenes using mixed lithium-zinc and lithium-cadmium combinations. Chem Commun 46 2862-2864. doi 10.1039/b924939g... 

The preparation and structure determination of ferrocene marked the beginning of metallocene chemistry Metallocenes are organometallic compounds that bear cyclo pentadiemde ligands A large number are known even some m which uranium is the metal Metallocenes are not only stucturally interesting but many of them have useful applications as catalysts for industrial processes Zirconium based metallocenes for example are the most widely used catalysts for Ziegler-Natta polymerization of alkenes We 11 have more to say about them m Section 14 15... 

The methods of preparation of ferrocene have been reviewed by Pauson and by Fischer. Ferrocene has been made by the reaction of ferric chloride with cyclopentadienylmagnesium bromide, by the direct thermal reaction of cyclopentadiene with iron metal, by the direct interaction of cyclopentadiene with iron carbonyl, by the reaction of ferrous chloride with cyclopentadiene in the presence of organic bases such as diethyl-amine, by the reaction of ferrous chloride with sodium cyclo-[lentadienide in liquid ammonia, and from cyclopentadiene and... 

Although not so generally applicable for the preparation of dicyclopentadienyl metal compounds as the sodium cyclopenta-dienide method, the amine procedure represents the simplest preparation of ferrocene. The amine procedure can also be employed for dicyclopentadienylnickel (about 80% yield), using nickel bromide obtained by the action of bromine on nickel metal powder and 1,2-dimethoxyethane as the solvent. The method of preparation given here is a modified version of that originally described. ... 

Tlie importance of bis(cyclopeniadienyl)irou (Fe(jj -C5H3)2( in the developmenl of organo-metallic chemistry has already been alluded to (p. 924). Tile compound, which forms orange crystals, mpl74°, has extraordinary thermal stability (>500°) and a remarkable structure which was unique when first established. It also has an extensive aromatic-lype reaction chernisiry which is reflected in its common name ferrocene The molecular structure of ferrocene in the ciysialline slac features two parallel cyclopentadienyl rings at one lime Ihese... 

The most notable chemistry of the biscylopen-tadienyls results from the aromaticity of the cyclopentadienyl rings. This is now far too extensively documented to be described in full but an outline of some of its manifestations is in Fig. 25.14. Ferrocene resists catalytic hydrogenation and does not undergo the typical reactions of conjugated dienes, such as the Diels-Alder reaction. Nor are direct nitration and halogenation possible because of oxidation to the ferricinium ion. However, Friedel-Crafts acylation as well as alkylation and metallation reactions, are readily effected. Indeed, electrophilic substitution of ferrocene occurs with such facility compared to, say, benzene (3 x 10 faster) that some explanation is called for. It has been suggested that. 

As shown in Table IV, the highest catalytic activity of metal halides used as Lewis acid for the alkylation reaction of ferrocene with 2 was observed in methylene chloride solvent. Among Lewis acids such as aluminum chloride, aluminum bromide, and Group 4 transition metal chlorides (TiCl4, ZrCU, HfCU), catalytic efficiency for the alkylation decrea.ses in the following order hafnium chloride > zirconium chloride > aluminum chloride > aluminum bromide. Titanium chloride... 

Effects of spacer groups on the formation and properties of the mixed-valence states of conjugated ferrocene dimers have been extensively studied by both electrochemical and spectroscopic methods. It should be noted that a characteristic feature in the electronic spectra of ferrocene dimers with conjugated spacer groups is the appearance of metal-to-ligand charge transfer (MLCT) bands in the neutral form as well as IT bands in the mixed-valence state. The dimer Fc — CH=CH — Fc... 

The ferrocenyldiphynylpropargyl cation, 77, has an intrinsic delocalization nature exhibiting a valence tautomerization band at 856 nm, and its nucleophilic trapping reactions give rise to the formation of ferrocenyldiphyenylallenes (173). The bis(acetylide) mixed-valence complexes of ferrocene and the Ru complex moiety, 78, also behave as a fulvene-cumulene structure, 79, showing a u(M=C = C—C) band at 1985 cm-1 (174). Related alleylidene and cumulenylidene complexes of transition metals have been reviewed by Bruce (175). 

Wagner and co-workers have reported the synthesis of ferrocene-bridged tris(l-pyrazolylborate) oligomeric systems (80) (Fig. 49).62 Such polymers are of interest, as they offer a multiplicity of options for tailoring the access space to a metal held by the tris(l-pyrazolylborate) ligand, as well as a means to electronically influence the environment of a transition metal.113,114... 

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