Macrobicyclic mechanism

The kinetics and mechanism of synthesis and decomposition of macrocyclic compounds are regarded as one of the most important aspects in the chemistry of these compounds. The majority of papers concern metal ions complexing with preliminarily synthesized macrocyclic ligands and metal ion substitutions by other metal ions in the preliminarily prepared complexes. Template synthesis, the most promising approach to the directed preparation of macrocyclic compounds with desired structures [17], plays a still more decisive role in the chemistry of macrobicyclic complexes with encapsulated metal ion. However, the literature contains only scarce data on the kinetics and the mechanism of the template synthesis of macrocyclic compounds because of the difficulties encountered in experimental determinations of kinetic and thermodynamic parameters, such as low product yields, nonaqueous media, high temperatures, and side reactions. 

A mechanism similar to that of Scheme 106 was also proposed for macrobicyclic cobalt(III) tris-cyclohexanediaminates [107]. 

The simple but rather useful molecular mechanics calculations were applied to both electron transfer kinetics and reduction potentials for a wide range of hexamine cobalt(III/II) complexes with primary, secondary, tertiary, and macrobicyclic amine ligands [237]. The redox potentials of the Co +/2+ couples varied from... 

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