Cobaltate resolution

The principle cost determinant in typical hydrolytic or phenolic resolutions is the cobalt catalyst, despite the relatively low catalyst loadings used in most cases and the demonstrated recyclability with key substrates. From this standpoint, recently developed oligomeric (salen)Co complexes, discussed earlier in this chapter in the context of the hydrolytic desymmetrization of meso-epoxides (Scheme 7.16), offer significant advantages for kinetic resolutions of racemic terminal epoxides (Table 7.3) [29-31]. For the hydrolytic and phenolic kinetic resolutions, the oligo-... 

Another application of salen ligands is the hydrolytic kinetic resolution of epoxides (Scheme 3). For this purpose cobalt complexes are efficient, and fiu-... 

It is noteworthy that, as early as 1929, Shibata and Tsuchida reported a kinetic resolution of rac-3,4-dihydroxyphenylalanine by selective oxidation of one enantiomer using a chiral cobalt complex [Co(en)3NH3Cl]Br2 as a catalyst [46,47]. Figure 12 shows a highly enantioselective addition of diisopropy-Izinc to 2-(ferf-butylethynyl)pyrimidine-5-carbaldehyde via an autocatalytic process in the presence of a chiral octahedral cobalt complex with ethylenedi-... 

For infrared spectroscopy, 20-50 mg of the cobalt-exchanged zeolite was pressed into a self-supporting wafer and placed into an infrared cell similar to that described by Joly et al. [21], Spectra were recorded on a Digilab FTS-50 Fourier-transform infrared spectrometer at a resolution of 4 cm-i. Typically, 64 or 256 scans were coadded to obtain a good signal-to-noise ratio. A reference spectrum of Co-ZSM-5 in He taken at the same temperature was subtracted from each spectrum. 

Fig. 13 Super-lattice of cobalt nanorods a Top view hexagonal b vue de cote c image k haute resolution...

Molecules having only a sulfoxide function and no other acidic or basic site have been resolved through the intermediacy of metal complex formation. In 1934 Backer and Keuning resolved the cobalt complex of sulfoxide 5 using d-camphorsulfonic acid. More recently Cope and Caress applied the same technique to the resolution of ethyl p-tolyl sulfoxide (6). Sulfoxide 6 and optically active 1-phenylethylamine were used to form diastereomeric complexes i.e., (-1-)- and ( —)-trans-dichloro(ethyl p-tolyl sulfoxide) (1-phenylethylamine) platinum(II). Both enantiomers of 6 were obtained in optically pure form. Diastereomeric platinum complexes formed from racemic methyl phenyl (and three para-substituted phenyl) sulfoxides and d-N, N-dimethyl phenylglycine have been separated chromatographically on an analytical column L A nonaromatic example, cyclohexyl methyl sulfoxide, did not resolve. 

Fanali, S., Ossicini, L., Foret, F., and Bocek, R, Resolution of optical isomers by capillary zone electrophoresis study of enantiomeric and distereoisomeric cobalt (III) complexes with ethylenediamine and amino acid ligands, /. Microcol. Sep., 1, 190, 1989. 

Composition Profile Measurement. Results of Zieba et al. (1997) will be given as an example of the measurement of solute distribution in an alloy undergoing a phase transformation. They studied discontinuous precipitation in cobalt-tungsten alloys, in which a Co-32 wt% W alloy was aged in the temperature range 875 K to 1025 K, and high spatial resolution X-ray microanalysis of thin foils by STEM was used to measure the solute distribution near the reaction front. 

The very high resolution for the ESR spectrum of cob(II)alamin in the enzyme system is undoubtedly due to the fact that all the coenzyme molecules are bound in an identical environment at the enzyme active site. This results in a homogeneous cobalt-benzimidazole geometry, because both identical binding sites, solvent, and solute molecules can no longer approach the Bia-molecule closely. In addition, the enzyme bound cob(II)alamin molecules are more isolated from one another and thus relaxation due to spin-spin interactions is less effective in broadening spectral lines. 

A third factor has been suggested for enhanced resolution of the Co(II) ESR spectrum, because in the enzyme the movement of the acetamide and propionamide side-chains of the corrin ring will be restricted. This restriction would diminish fluctuations in the magnetic environment of the cobalt. 

Nuclear magnetic resonance studies on spin labeled derivatives are not extremely useful due to the paramagnetism of the molecule. However, the NMR spectrum of spin labeled methylcobinamide confirms that the nitroxyl function is coordinated to the cobalt. It is possible in this compound to obtain good resolution of the methyl group resonance. 

Field et al. [747] used ICP high-resolution mass spectrometry to determine vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, cadmium, and lead in seawater. Each analysis required 50 p,l sample and a 6 minute analysis time. 

Carbonylative kinetic resolution of a racemic mixture of trans-2,3-epoxybutane was also investigated by using the enantiomerically pure cobalt complex [(J ,J )-salcy]Al(thf)2 [Co(CO)4] (4) [28]. The carbonylation of the substrate at 30 °C for 4h (49% conversion) gave the corresponding cis-/3-lactone in 44% enantiomeric excess, and the relative ratio (kre ) of the rate constants for the consumption of the two enantiomers was estimated to be 3.8, whereas at 0 °C, kte = 4.1 (Scheme 6). This successful kinetic resolution reaction supports the proposed mechanism where cationic chiral Lewis acid coordinates and activates an epoxide. 

Among protein aromatic groups, histidyl residues are the most metal reactive, followed by tryptophan, tyrosine, and phenylalanine.1 Copper is the most reactive metal, followed in order by nickel, cobalt, and zinc. These interactions are typically strongest in the pH range of 7.5 to 8.5, coincident with the titration of histidine. Because histidine is essentially uncharged at alkaline pH, complex-ation makes affected proteins more electropositive. Because of the alkaline optima for these interactions, their effects are most often observed on anion exchangers, where complexed forms tend to be retained more weakly than native protein. The effect may be substantial or it may be small, but even small differences may erode resolution enough to limit the usefulness of an assay. 

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