Alkali metal cation

Table A2.3.2 Halide-water, alkali metal cation-water and water-water potential parameters (SPC/E model). In the SPC/E model for water, the charges on H are at 1.000 A from the Lennard-Jones centre at O. The negative charge is at the O site and the HOH angle is 109.47°.

Fig. 10. Unpolarized Raman spectra (T = 300 K) for solid Ceo, KaCeo, RbsCeo, NaeCeo, KaCco, RbeCeo and CseCeo [92, 93], The tangential and radial modes of Ag symmetry are identified, as are the features associated with the Si substrates. From the insensitivity of these spectra to crystal structure and specific alkali metal dopant, it is concluded that the interactions between the Cao molecules are weak, as are also the interactions between the Cao anions and the alkali metal cations.

The one-pot synthesis of 9 described above appears to afford only modest yields of azacrowns. One might wonder why any crown at all would be formed under non-high dilution conditions intended to yield only open-chained material. Vogtle suggests that this can be explained in terms of template, steric and entropy effects . These factors are of doubtless significance, but it is interesting to note that in the synthesis of poly-azamacrocycles, Richman and Atkins found that there was no significant template effect observed. The question of the template effect in Ihe syntheses of 9 has recently been addressed by Kulstad and Malmsten They conclude that the formation of 9 is assisted by the presence of alkali metal cations. 

The work of Hyatt on cyclotriveratrylene—derived octopus molecules contrasts with this. Of course, these species have the advantage of ligand directionality absent in the benzene-derived octopus molecules. Except for the shortest-armed of the species (i.e., n = 1), all of the complexing agents (i.e., n = 2—4) were capable of complexing alkali metal cations. Synthesis of these species was accomplished as indicated below in Eq. (7.7). These variations of the original octopus molecules were also shown to catalyze the reaction between benzyl chloride and potassium acetate in acetonitrile solution and to effect the Wittig reaction between benzaldehyde and benzyltriphenylphos-phonium chloride. 

The proportion of hydrochloric acid in the mobile phase was not to exceed 20%, so that complex formation did not occur and zone structure was not adversely affected. An excess of accompanying alkaline earth metal ions did not interfere with the separation but alkali metal cations did. The hthium cation fluoresced blue and lay at the same height as the magnesium cation, ammonium ions interfered with the calcium zone. 

The yellow [S4N5] anion (5.26) was first reported in 1975 from the methanolysis of Me3SiNSNSiMc3. It can also be prepared by the treatment of S4N4 with certain nucleophiles, e.g., secondary amines or azide salts of small alkali metal cations (Eq. 5.16). The reaction of (NSC1)3 with dry liquid ammonia at -78°C also generates [NH4][S4N5] in ca. 50% yield." ... 

Figure 4.11 Molecular structures of typical crown-ether complexes with alkali metal cations (a) sodium-water-benzo-I5-crown-5 showing pentagonal-pyramidal coordination of Na by 6 oxygen atoms (b) 18-crown-6-potassium-ethyl acetoacetate enolate showing unsymmelrical coordination of K by 8 oxygen atoms and (c) the RbNCS ion pair coordinated by dibenzo-I8-crown-6 to give seven-fold coordination about Rb.

Another group of very effective ligands that have recently been employed to coordinate alkali metal cations are the macrobicyclic polydentate ligands that J.-M. Lehn has termed... 

In contradistinction to this, weak ferromagnetism has been observed in a number of chloro and bromo complexes of the type M2[CrX4] (M = a variety of protonated amines and alkali metal cations, X = Cl, Br), which are analogous to previously known copper(II) complexes (p. 1192). They have magnetic moments at room temperature in the region of 6BM (compared... 

In mimicking this type of function, noncyclic artificial carboxylic ionophores having two terminal groups of hydroxyl and carboxylic acid moieties were synthesized and the selective transport of alkali metal cations were examined by Yamazaki et al. 9 10). Noncyclic polyethers take on a pseudo-cyclic structure when coordinating cations and so it is possible to achieve the desired selectivity for specific cations by adjusting the length of the polyether chain 2). However, they were not able to observe any relationship between the selectivity and the structure of the host molecules in an active transport system using ionophores 1-3 10). (Table 1)... 

By considering the stability constant and the lipophilicity of host molecules, Fyles et al. synthesized a series of carboxylic ionophores having a crown ether moiety and energetically developed the active transport of alkali metal cations 27-32). Ionophores 19-21 possess appropriate stability constants for K+ and show effective K+-selective transports (Fig. 5). Although all of the corresponding [15]crown-5 derivatives (22-24) selectively transport Na+, their transport rates are rather slow compared with... 

A certain crown ether having additional coordination sites for a trasition metal cation (71) changes the transport property for alkali metal cations when it complexes with the transition metal cation 76) (Fig. 13). The fact that a carrier can be developed which has a reversible complexation property for a transition metal cation strongly suggests that this type of ionophore can be applied to the active transport system. 

The alkali metal cations are identified by flame tests (Figure C). 

MiNbC F compounds have a NaC 1-type structure, and are stable only in the case of lithium due to the steric similarity between the lithium ion and Nb3. In the case of other alkali metal cations with larger ionic diameters, the M4Nb04F compounds decompose yielding orthoniobates and simple fluorides of alkali metals, as follows ... 

The variation that exists in the 0 F ratio of MMe6Oi5F-type compounds enables isomorphic replacement of alkali metal cations by other cations with appropriate radii. For instance, a copper-containing compound, Cuo.6Nb6Oi4 6F( 4, which crystallizes in a LiNbeOisF type structure, was obtained [255]. 

The nature of outer-sphere alkali metal cations can actually define the ionic equilibrium and also has an affect on complex anions. Fig. 77 illustrates the influence of the cationic surrounding on the wave numbers. 

A slight but systematic decrease in the wave number of the complexes bond vibrations, observed when moving from sodium to cesium, corresponds to the increase in the covalency of the inner-sphere bonds. Taking into account that the ionic radii of rubidium and cesium are greater than that of fluorine, it can be assumed that the covalent bond share results not only from the polarization of the complex ion but from that of the outer-sphere cation as well. This mechanism could explain the main differences between fluoride ions and oxides. For instance, melts of alkali metal nitrates display a similar influence of the alkali metal on the vibration frequency, but covalent interactions are affected mostly by the polarization of nitrate ions in the field of the outer-sphere alkali metal cations [359]. 

The anions MeF6 and X approach each other closely to form the heptacoordinated complex MeF6X(n+1)", or separate from one another, according to the polarization potential of the outer-sphere cation (alkali metal cation -M+). This process is unique in that the mode frequencies of the complexes remain practically unchanged despite varying conditions. This particular stability of the complexes is due to the high charge density of Ta5+ and Nbs+. 

The appearance of the seventh ligand (Xn ) predominantly in the first coordination sphere of the complex or outside of the complex depends on the polarization potential of the alkali metal cation, M+, and on the polarity of the seventh anion, Xn". Increased polarity of the anion favors its entering into the first coordination sphere of the complex ion. 

Chai and Zhong [602] investigated the melting properties of molten systems containing K2TaF7 and different alkali metal cations with respect to the optimization of the sodium reduction process. It was shown that the specific... 

In all cases some sensitivity to hydrogen ions remains in any potentiometric determination with these modified glass electrodes the hydrogen ion concentration of the solution must be reduced so as to be not more than 1 per cent of the concentration of the ion being determined, and in a solution containing more than one kind of alkali metal cation, some interference will be encountered. 

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