Chemistry

Coordination Chemistry of Macrocyclic Compounds by Gordon A. Melson (auth.), Gordon A. Melson (eds.)

By Gordon A. Melson (auth.), Gordon A. Melson (eds.)

Chemists were conscious of the lifestyles of coordination compounds con­ taining natural macrocyclic ligands because the first a part of this century ; despite the fact that, merely in past times few years have they increased learn into the chemistry of those compounds. the growth was once initiated within the early Sixties through the synthesis and characterization of compounds containing a few new macrocyclic ligands. The synthesis of compounds which can function version platforms for a few usual items containing huge jewelry as ligands supplied the most objective for the early growth of analysis attempt; certainly, a recurrent subject in the back of a lot of the suggested chemistry has been the analogy among artificial macrocyclic compounds and plenty of natural-product structures. extra lately, the emphases of said study have ranged over the entire spectrum of chemistry, and the variety of guides that debate macrocyclic chemistry has elevated at a dramatic price. the finished study has been said in numerous journals during the global yet there was no prior try to carry the main advancements jointly below one conceal. This publication, for this reason, makes an attempt to fulfill the necessity for a unmarried resource during which there's either a suite and a correlation of knowledge in regards to the coordination chemistry of macrocyclic compounds. The chapters during this e-book talk about quite a few facets of macrocyclic chemistry, and whereas those chapters as a complete represent an in-depth survey of the state-of­ the-art of the sphere, each one bankruptcy is written as a whole unit.

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1-6,12) There is no doubt that the metal ion plays an important role in directing the steric course of the reaction. Lindoy and Busch(6) have discussed this role in terms of coordination template effects. If the directive influence of the metal ion controls the steric course of a sequence of stepwise reactions, the kinetic template effect is considered to be operative. If the metal ion perturbs an existing equilibrium in the organic system by preferential coordination with one of the components, and by this coordination the required product is obtained as its metal complex, then the thermodynamic (or equilibrium) template effect is considered to be operative.

Sadasvian and Endicott(2S) reported that the reaction of Fe(en)a(CIO,)2 with dry acetone at room temperature results in the formation of small transparent crystals on the walls of the container. After a period of approximately 36 hr, the crystals were removed by filtration, washed with acetone, and separated from a black precipitate by decanting in the presence of ethanol. A 63% yield of Me6[14]4,1l-dieneN,·2HCIO, was obtained. The complexes [NiL]tCIO,)2, [CuL](CIO')2' [ZnL(H20)CI]CIO" [CoLCOa]CIO" and [CoL](CIO')2 (L = Mes[14]4,II-dieneN,) were prepared from the dihydroperchlorate salt by treatment with the appropriate metal ion in basic solution.

One potential disadvantage of the complexation reaction approach is that the synthesis of the organic macrocycle often results in low yields of the desired product. In attempts to increase the yield of the macrocycle and reduce side reactions such as polymerizations, the final ring closure reaction in a stepwise synthesis is often carried out under conditions of high dilution. <2o,21) In spite of the conditions, the yield of [14]aneN4 was very low ("" 5%). <25,2S) In spite of problems which may be encountered during the synthesis of the macrocyclic ligands, the complexation reaction approach has been extensively employed for the synthesis of complexes containing synthetic macrocycles, in particular, cyclic tetramines, cyclic polyethers (crowns), and macrobicyclic ligands such as cryptands (see Chapter 9 for a discussion of complexes containing crowns and cryptands).

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