Monosubstituted Ferrocene

The first monosubstituted ferrocene derivatives containing chiral amino-sulfide backbones in the side chain were reported by Bonini et These... 

Chiral ferrocenes form a class of powerful and useful chiral hgands, and a number of methods are available for their enantioselective synthesis. The introduction of a second substituent via directed metallation is a simple and powerful way to make disubstituted ferrocenes with planar chirality from simple, achiral monosubstituted ferrocenes. Chiral... 

Several generalizations are made on the basis of such data as in Table I. For instance, the two rings tend to absorb independently of one another10 that is, no conjugation of one ring to another. Nesmeyanov has also noted that while intensities of bands in the 220-600 m region increased from ferrocene to monosubstituted ferrocenes to heteroannularly disubstituted ferrocenes, the opposite is true in the 180-220 mjx region. 

The method has the advantage that it ensures formation of pure monosubstituted ferrocene, free of the disilylated products. This procedure has been used also for lithiation of a cyclopentadienylcobalt derivative, which showed ferrocene-like behavior (R = Ph) (128, 129) ... 

Since monosubstituted ferrocenes do not have a potential identical to that for ferrocene itself, the surface reagent may be enough different that its oxidizing power can be greater. 

Ferrocene-containing co-polyesters, preparation, 12, 350 Ferrocene-containing liquid crystals dendrimers, 12, 235 disubstituted ferrocenes, 12, 227 hydrogen-bonded ferrocene derivatives, 12, 234 monosubstituted ferrocenes, 12, 222 polycatenar ferrocenes, 12, 234 properties, 12, 221... 

Monosubstituted acetylenes, polymerization, 11, 559 Monosubstituted ferrocenes, properties, 12, 222 Monothiolato compounds, in mono-Cp Ti(IV) complexes,... 

Following the paper by Reed and Tabrizi, Mandelbaum and Cais (135) reported the mass spectra of six monosubstituted ferrocenes having a carbonyl group in the a-position to the cyclopentadienyl ring. In addition... 

Since monosubstituted ferrocenes contain only two distinct homo-annular positions, the ferrocenes system would appear to be an easier one than benzene for analysis of PMR effects. 

Differentiation of the Hj, 5 and Hj 4 chemical shift values was possible for all monosubstituted ferrocenes with the exception of the alkylferrocenes, which required use of a Varian 220 MHz spectrometer for resolution (77). The results are tabulated in Table III. It is particularly interesting that the... 

PMR Chemical Shift Values (ppm) of Monosubstituted Ferrocenes [XCsH4FeC5H5] from TMS - ... 

Butter and Beachell (11) utilized a somewhat different method of estimating the electron density apportioned to the unsubstituted ring. A plot of shielding values of eight monosubstituted ferrocenes vs. Hammett s a constants was obtained for both the substituted and unsubstituted ring protons. From the slopes of these plots the authors obtained p values of... 

Exhaustive mercuration of ferrocene with mercury(ii) trifluoroacetate, Hg(OCOCF3)2, is another possibility to synthesize polyhalogenated ferrocenes [37]. The reaction of deca(trifluoroacetato-mercuri)ferrocene, Fe[C5(Hg-OCOCF3)5]2, with the trihalides KBr3 and KI3 can be used to prepare Fe(C5Br5)2 and Fe(C5l5)2, respectively monosubstituted ferrocenes, Fc-R, react in an analogous manner (Scheme 5-5) ... 

Fig. 9-3. Monosubstituted ferrocene-containing thermotropic liquid crystals.

Other monosubstituted ferrocenes have been reported by Imrie and co-workers. For example, the complex shown in Figure 54 is clearly less anisotropic than the original described by Malthete and Billard, and shows a nematic phase at just above... 

Recent progress in material science, notably with the development of new materials exhibiting blue phases, has generated a renewed interest in the incorporation of the functional properties with the unique structure of frustrated phases. Synthesis of a monosubstituted ferrocene-based chiral Schiff s base derivative which exhibits TGBA and blue phases has been reported [17] (Fig. 9). Other metallomesogens leading to blue phases have been found for palladium complexes [18] (Fig. 10). Optically active materials incorporating... 

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