Cryptate complexes synthesis

Graf E, Lehn JM (1975) Synthesis and cryptate complexes of a spheroidal macrotricychc ligand with an octahedrotetrahedral coordination. J Am Chem Soc 97 5022-5024... 

The subject matter of this chapter will be subdivided into sections concerning template synthesis of the complexes structural and thermodynamic properties of the complexes with synthetic cyclic polyamines complexes with mixed-donor macrocycles reactivity of the complexes cryptates and complexes with phthalocyanines and porphyrins. 

Dietrich, B., Dilworth, B., Lehn, J.-M., etal, Anion cryptates Synthesis, crystal structures, and complexation constants of fluoride and chloride inclusion complexes of polyammonium macrobicyclic ligands. Helv. Chim. Acta 1996, 79, 569-587. 

Lehn, J.-M. Pine, S. H. Watanabe, E. I. Willard, A. K. Binuclear cryptates. Synthesis and binuclear cation inclusion complexes of bis-tren macrobicyclic ligands, J. Am. Chem. Soc. 1977, 99, 6766-6768. 

The cryptands were first prepared in 1969 and form a series of well-defined complexes (cryptates) with alkali and alkaline-earth cations. In this chapter the synthesis of the first cryptand, 8, a macrobicyclic ligand, will be described1,2. The schematic representation (Fig. 5.1) shows that one deals with a multi-step synthesis. The major drawback of this approach is the rather large number of synthetic steps, but the route offers the advantage of being able to construct unsymmetrical compounds (A B C). 

Results concerning other cryptates incorporating chromophoric groups are presented in the following. The synthesis of the Eu3+ complex of ligand... 

Extensive studies on metal (Ni or Fe) promoted oxidative dehydrogenations of this and related systems have been reported, the latter paper containing a note on the nomenclature of these complexes which appears to have become rather confused. Related complexes,a new synthesis of cyclam as its Ni complex, and an investigation of Li salt complexes of cyclam by i.r. measurements have also been reported. Mononuclear cryptates, with a wide variety of metal iodides and chlorides, and dinuclear cryptates, with AgN03 and HCOgTl, involvingthe macrotricyclic ligand (500) are discussed. 8i... 

Many organic reactions which involve ionic species involve the cations associated with the reactive anions, even though most of the attention is focused on the latter. Some reactions, like the displacement of bromide by cyanide in the synthesis of a cyano-alkane [5] (see Eq. 7.2), appear to involve the cation in only the most peripheral way. In the above example, replacing sodium cyanide by tetrabutylammonium cyanide [6,7] or the 18-crown-6 complex of potassium cyanide does not alter the course of the reaction [8, 9], only its rate. There are, however, quite a few examples now available of alterations in the course of the reaction in the presence of crown ether, cryptate, or ammonium salts. 

Rare earth cryptates (table 5) are more stable than coronates and are highly kinetically inert towards dissociation in aqueous solutions. They can therefore be studied in water, but hydrolysis hinders their synthesis in this solvent. On the contrary, the preparation of unsolvated 1 1 complexes requires anhydrous conditions (Gansow and Triplett, 1981). The hydrated lanthanide salt solutions in... 

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