Sodium cation effects

A typical absorption curve for vitreous siUca containing metallic impurities after x-ray irradiation is shown in Eigure 12. As shown, the primary absorption centers are at 550, 300, and between 220 and 215 nm. The 550-nm band results from a center consisting of an interstitial alkah cation associated with a network substituent of lower valency than siUcon, eg, aluminum (205). Only alkaUes contribute to the coloration at 550 nm. Lithium is more effective than sodium, and sodium more effective than potassium. Pure siUca doped with aluminum alone shows virtually no coloration after irradiation. The intensity of the band is deterrnined by the component that is present in lower concentration. The presence of hydrogen does not appear to contribute to the 550-nm color-center production (209). 

It is interesting to note that although the first examples of template effects were observed in nitrogen macrocycles (see chapter 2) no template effect appears to operate in the synthesis of 72. Richman and Atkins note this in their original report . The authors replaced the sodium cation with tetramethylammonium cations and still obtained greater than 50% yield of tetra-N-tosyl-72. Shaw considered this problem and suggested that because of the bulky N-tosyl groups, .. . the loss of internal entropy on cyclization is small He offered this as an explanation for the apparent lack of a template effect in the cyclization. 

Cholanic acid also possesses the ability of transporting cations across a lipophilic membrane but the selectivity is not observed because it contains no recognition sites for specific cations. In the basic region, monensin forms a lipophilic complex with Na+, which is the counter ion of the carboxylate, by taking a pseudo-cyclic structure based on the effective coordination of the polyether moiety. The lipophilic complex taken up in the liquid membrane is transferred to the active region by diffusion. In the acidic region, the sodium cation is released by the neutralization reaction. The cycle is completed by the reverse transport of the free carboxylic ionophore. 

Adsorption enthalpies and vibrational frequencies of small molecules adsorbed on cation sites in zeolites are often related to acidity (either Bronsted or Lewis acidity of H+ and alkali metal cations, respectively) of particular sites. It is now well accepted that the local environment of the cation (the way it is coordinated with the framework oxygen atoms) affects both, vibrational dynamics and adsorption enthalpies of adsorbed molecules. Only recently it has been demonstrated that in addition to the interaction of one end of the molecule with the cation (effect from the bottom) also the interaction of the other end of the molecule with a second cation or with the zeolite framework (effect from the top) has a substantial effect on vibrational frequencies of the adsorbed molecule [1,2]. The effect from bottom mainly reflects the coordination of the metal cation with the framework - the tighter is the cation-framework coordination the lower is the ability of that cation to bind molecules and the smaller is the effect on the vibrational frequencies of adsorbed molecules. This effect is most prominent for Li+ cations [3-6], In this contribution we focus on the discussion of the effect from top. The interaction of acetonitrile (AN) and carbon monoxide with sodium exchanged zeolites Na-A (Si/AM) andNa-FER (Si/Al= 8.5 and 27) is investigated. 

Solvents, specifically surrounding the sodium cation, lower its effect. In the presence of a crown ether, including and blockading the sodium cation, the rate of the final product formation is entirely restored. 

Electroreductive one-electron initiation of cyclization was described for the series of E,E-, 1-dibenzoyl-l,6-heptadiene and its derivatives (Roh et al. 2002, Felton and Bauld 2004). In this case, the catalytic effect was also observed (the actual consumption of electricity was substantially less than theoretical). The same bis(enones) can also be cyclized on the action of the sodium salt of chrysene anion-radical in THF, but with no catalytic effect. Optimum yields were obtained only when 70-120 mol% of the initiator was used, relative to a substrate (Yang et al. 2004). The authors suggest that tight ion pairing of the sodium cation with the product anion-radical in THF (which is a somewhat nonpolar solvent) slows down the intermolecular electron transfer to the bis(enone) molecules. Such an electron transfer would be required for chain propagation. 

Anion effects have been observed especially in relation to dissolution of the cation complexes in media of low polarity. Soft organic and inorganic anions (phenates, thiocyanate, permanganate etc) generally allow ready dissolution the pier ate anion has been much used (62, 66). The interaction between the anion and the complexed cation may affect the stability of the complex. Ion pairing may occur when the anion can contact the complexed cation, as in the case of macrocyclic complexes, where approach of the anion from top and bottom is possible. This is observed in the RbNCS complex of IS, but not in its NaNCS complex, as shown by the crystal structure data (100). With bromide as anion both a complexed ion pair and a complexed sodium cation are found in the solid state for (15, NaBr) (118). 

Two sets of patterns were calculated for each structure with and without sodium cations (Table II). These results indicated that the effect of the cations could be ignored. This is confirmed by actual patterns for the Na and H forms of a synthetic mordenite. Because mordenite has a low cation content, cation effects on peak intensities should be minimal. 

Reduction of ketones. Reduction of ketones with metals in an alcohol is one of the earliest methods for effecting reduction of ketones, and is still useful since it can proceed with stereoselectivity opposite to that obtained with metal hydrides.1 An example is the reduction of the 3a-hydroxy-7-ketocholanic acid 1 to the diols 2 and 3. The former, ursodesoxycholic acid, a rare bile acid found in bear bile, is used in medicine for dissolution of gallstones. The stereochemistry is strongly dependent on the nature of the reducing agent (equation I).2 Sodium dithionite and sodium borohydride reductions result mainly in the 7a-alcohol, whereas reductions with sodium or potassium in an alcohol favor reduction to the 7p-alcohol. More recently3 reduction of 1 to 2 and 3 in the ratio 96 4 has been achieved with K, Rb, and Cs in f-amyl alcohol. Almost the same stereoselectivity can be obtained by addition of potassium, rubidium, or cesium salts to reductions of sodium in t-amyl alcohol. This cation effect has not been observed previously. 

One molecule of 391 displays a positive cooperative effect in binding two sodium cations when 391 is treated with sodium perchlorate, whereas 391 generates a 1 1 complex with K+ [360], The photocyclomerization was demonstrated... 

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