Cations and crown ethers

Very stable complexes can be formed when there is a good match between cation and crown ether not only with respect to size but also with respect to charge. This is apparent from the work of Cram s group, who examined crown ethers with additional anionic binding sites. For example, they found the monovalent ligand [64] to form extremely stable 1 1 complexes with K+. With Ba2+, [64] forms very stable 2 1 complexes. The bivalent ligand [65] binds... 

The hole-size relationship between cations and crown ethers has been a part of the lore in the cation binding area for nearly two decades. Although, to our knowledge, no formal definition of this principle has ever been offered, the general concept seems to be that cation binding will be optimized when the cation diameter and macrocycle cavity size are identical. A simple consequence of this concept is the notion that 15-crown-5 is selective (binds more strongly) for Na+ over K+. We have measured the homogeneous (equilibrium) stability constants for the reaction... 

Starks et al. [183] have addressed several questions regarding the mechanistic details of SLPTC, and those include what are the mechanisms of transport of anions from the solid phase to the organic phase, the mechanisms of formation of reactive ion pairs, the mechanisms of exchange of product anions located in the organic phase with reactant anions located in the solid phase, the effects of particle size on the rates of reaction, the mechanistic differences between quaternary cation and crown ethers as PT catalysts, and the mechanistic role of small quantities of water in SLPTC. Obviously, the behavior of the active ion pairs or catalytic intermediates is important in realizing the mechanism of SLPTC. 

Ligands for the complexation of two different metal cations should possess cavities of different nature, such as tetradentate ligands for transition metal cations and crown ether type cavities for hard cations like alkali or alkaline earth metal cations [ref 6]. 

Ever since Petersen reported the complexing ability of the crown ether with alkali, alkaline earth and other cations, crown ether became a major subject for researchers. This is due to the fact that crown ether possesses the ability to form complexes with a variety of inorganic salts and also the ability to solubilize these salts in aprotic solvents The complexation between metal cation and crown ether is believed to involve ion-dipole interactions and therefore is similar in nature to ordinary solvation. In addition, crown ether/metal cation complexes can serve as catalysts in reactions involving ionic intermediates. Polymerization of diene with crown ether/metal cation complexes is a typical example of this subject, since this reaction involves ionic intermediates. The detailed information including a brief history, chemical properties of crown ether and its application in the anionic polymerization and copolymerization have been discussed. 

In Pedersen s early experiments, the relative binding of cations by crown ethers was assessed by extraction of alkali metal picrates into an organic phase. In these experiments, the crown ether served to draw into the organic phase a colored molecule which was ordinarily insoluble in this medium. An extension and elaboration of this notion has been developed by Dix and Vdgtle and Nakamura, Takagi, and Ueno In efforts by both of these groups, crown ether molecules were appended to chromophoric or colored residues. Ion-selective extraction and interaction with the crown and/or chromophore could produce changes in the absorption spectrum. Examples of molecules so constructed are illustrated below as 7 7 and 18 from refs. 32 and 131, respectively. 

Reaction of Na2Se and Na2Sc2 with Se in the presence of ethanolic solutions of tetraalkyl-ammonium halides and catalytic amounts of I2 yields dark green or black crystalline polyselenides (jc = 3,5-9) depending on the conditions used and the particular cation selected. Tetraphenylphosphonium salts and crown ether complexes of alkali or alkaline earth cations in dimethylformamide solution can also be used. " )... 

Inspired by the separation ability of cyclic selectors such as cyclodextrins and crown ethers, Malouk s group studied the synthesis of chiral cyclophanes and their intercalation by cation exchange into a lamellar solid acid, a-zirconium phosphate aiming at the preparation of separation media based on solid inorganic-organic conjugates for simple single-plate batch enantioseparations [77-80]. 

Beside four-coordinate Be2+ structures, a couple of five-coordinate structures are known, e.g., Dehnicke s [BeCl(12-crown-4)]+ (179). The combination of beryllium cations and different crown ethers is of particular interest, not only because the Nobel Prize was awarded in part for the development of crown ethers (15), but also because crown ethers are common building blocks in all kinds of chemistry (180,181), with a wide range of applications. Since Be2+ is the smallest metal ion, the binding modes of Be2+ and crown ethers can lead to unexpected structural motifs. 

Smaller, hard cations, such as alkyltrimethylammonium salts and crown ether-cation complexes, will promote the elimination of dichlorocarbene to form a hard ion pair of type Q+C1 . 

The crown ether, 18-crown-6 acts as a phase transfer catalyst and gets the anion into the organic phase. On coordination with a metal cation the crown ethers convert the metal ion into a species with a hydrocarbon like exterior. The crown ether. 

H and 13C NMR have also been widely used to study the binding of alkylammonium cations to crown ethers. The shift in substrate proton resonances can give detailed information of the preferred structure of the complex. This is particularly important in the study of chiral recognition by asymmetric receptors (79CSR85) (Section 5.21.3.2.2) and also the development of bioorganic models and catalysts (Section 5.21.5.1.1). 

Selective complexation of cations by crown ethers 17 [lb, lg] and calixarenes 18 [If] depending on the rings size was proposed to be used in sensors. 

By analogy with cation complexing crown ethers like 47-50, attachment of a defined number and type of Lewis acids to a rigidified molecular scaffold in such a way that their electron-efficient sites are... 

Polyethers. Polyethers such as polyethylene oxide (PEO) and polypropylene oxide (PPO) have been used for ESI-MS calibration [10,11,19]. The predominant ions for these calibrants are cation attachments, and sodium attachment is frequently observed, due to traces of sodium in solvents and glassware. The positive-ion ESI mass spectra of PEO and PPO are characterized by abundant [M + nNa]n+ and some [M + ] + species. Macrocyclic polyethers and crown ethers were also used as ESI-MS calibrants [11]. In general, nonderivatized polyethers show the following drawbacks when used as calibrations solutions (1) they are difficult to flush out of the ion source, (2) they generate complex mass spectra resulting from the presence of several different cation sources, and... 

Apart from their obvious utility in separating mixtures of cations,68 crown ethers have found much use in organic synthesis (see the discussion on p. 363). Chiral crown ethers have been used for the resolution of racemic mixtures (p. 121). Although crown ethers are most frequently used to complex cations, amines, phenols, and other neutral molecules have also been complexed69 (see p. 133 for the complexing of anions).70... 

The results (Table 10) show that the cryptands could act to produce carrier-mediated facilitated diffusion and there was no transport in the absence of the carrier. The rate of transport depended upon the cation and carrier, and the transport selectivity differed widely. The rates were not proportional to complex stability. There was an optimal stability of the cryptate complex for efficient transport, logKs 5, and this value is similar to that for valinomycin (4.9 in methanol). [3.2.2] and [3.3.3] showed the same complexation selectivity for Na+ and K+ but opposing transport selectivities. The structural modification from [2.2.2] to [2.2.C8] led to an enhanced carriage of both Na+ and K+ but K+ was selected over Na+. The modification changes an ion receptor into an ion carrier, and indicates that median range stability constants are required for transport. Similar, but less decisive, results have been found in experiments using open-chain ligands and crown ethers.498... 

Cathechol sulfate — see 2,2-dioxide under 1,3,2-Benzodioxathiole Cation inhibition crown ethers and, 7, 757 Cations... 

Gas phase studies reveal size selective effects on binding of ammonium cations to crown ethers and acyclic analogs [2.111]. 

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