Clathrochelates decomposition

In the absence of F ion acceptors, a clathrochelate is not formed and the reaction completed at a stage of cis-addition of the protonated dioxime to a square-planar macrocycle. With certain dioximes (H2NX and H2Dm), in the absence of the base the reaction yields a mixture of symmetric clathrochelates. In other cases, only a mixture of decomposition products has been formed [64]. 

Sufficient physicochemical parameters of clathrochelates have also been gained from the data on kinetics and the mechanism of their decomposition both in solution and in the gas phase. Moreover, such results provide additional information about the complexation mechanism. 

The use of kinetic and thermodynamic approaches along with physicochemical and X-ray diffraction data, as well as their comparison with earlier results for complexes with synthetic macrocyclic ligands, have allowed one to make sufficiently well-grounded conclusions about the mechanisms of synthesis and decomposition of clathrochelates. 

The iron(II) clathrochelate formation schemes are also confirmed by investigations on the kinetics of their decomposition in solution. In aqueous solution of FeD3(BOH)2 complexes, it is equilibrium... 

The temperature-dependent decomposition rate constants of the clathrochelate complexes can be measured providing that the proton... 

The most abundant ionic species arising from unimolecular decomposition of FeD3(BOH)2 clathrochelates. 

Two irreversible electron-transfer waves were detected in the potential range from 1900 to 0.0 mV at Hi/2 = 1100 and Eh2° = 1700 mV for clathrochelate [ZnDm i(ttnCr)2] cation and free [H2Dm3(ttnCr)2]2 ligand (Table 41). The first oxidation process corresponded to the redox couple, followed by decomposition of... 

---