18-Crown metal complexes

Further considerations. It needs to be noted that the stoichiometry of a given crown-metal complex is not only influenced by ring size a range of other factors which include the charge density on the metal, the nature of the anion, and the relative strain energies of the crown in different conformations may all make a contribution. 

Shinkai, S., Ishira, M., Ueda, K., and Manabe, O. Photoresponsive crown ethers. Part 14. Photoregulated crown-metal complexation by competitive intramolecular tailfammonium)-biting./. Chem. Soc. Perkin Trans. 2 1985, 511-518. 

ON-OFF-SWITCHED CROWN-METAL COMPLEXATION BY PHOTOINDUCED INTRAMOLECULAR TAIL (AMMONIUM)-BITING... 

Phase-transfer catalysis succeeds for two reasons. First, it provides a mechanism for introducing an anion into the medium that contains the reactive substrate. More important, the anion is introduced in a weakly solvated, highly reactive state. You ve already seen phase-transfer catalysis in another fonn in Section 16.4, where the metal-complexing properties of crown ethers were described. Crown ethers pennit metal salts to dissolve in nonpolai solvents by sunounding the cation with a lipophilic cloak, leaving the anion free to react without the encumbrance of strong solvation forces. 

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.

Novel electron-transfer reactions mediated by alkali metals complexed with crown ethers as macrocyclic ligands 98ACR55. 

In this chapter we discuss host-guest complexes of arenediazonium salts with crown ethers and related compounds. Transition metal complexes of arenediazonium ions are treated together with those of dinitrogen and of diazoalkanes in our second book (Zollinger, 1995, Sec. 10.1). 

Crown ethers may also be used to functionalize salicylideneimine complexes.1179 The crown ether-functionalized tetra-t-butyl-salicylideneimines are useful in studies on the selective com-plexation and transport of cations (e.g., Na+ and K+). 4,5-Bis(3,5-di-/-butylsalicylideneimino) benzo-18-crown-6 coordinates Ni11 via the Schiff base N202 donor system and K+ or Cs+ at the crown site.1180 These Ni-alkali metal complexes are able to transport amino acids from acidic aqueous solution to pure water. 

An enormous variety of solvates associated with many different kinds of compounds is reported in the literature. In most cases this aspect of the structure deserved little attention as it had no effect on other properties of the compound under investigation. Suitable examples include a dihydrate of a diphosphabieyclo[3.3.1]nonane derivative 29), benzene and chloroform solvates of crown ether complexes with alkyl-ammonium ions 30 54>, and acetonitrile (Fig. 4) and toluene (Fig. 5) solvates of organo-metallic derivatives of cyclotetraphosphazene 31. In most of these structures the solvent entities are rather loosely held in the lattice (as is reflected in relatively high thermal parameters of the corresponding atoms), and are classified as solvent of crystallization or a space filler 31a). However, if the geometric definition set at the outset is used to describe clathrates as crystalline solids in which guest molecules... 

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