The influence of structural factors on the solvation and coordination unsaturation of metal complexes of several structurally related alkyl substituted dipyrrolylmethenes-2,2' and porphin

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The literature data and new results of calorimetric studies of the solution of copper(II), cobalt(II), zinc(II), nickel(II), and mercury(II) complexes with 3,3',4,4',5,5'-hexamethyldipyrrolylmethene-2,2'; 3,3',5,5'-tetramethyl-4,4'-diethyldipyrrolylmethene-2,2'; 3,3',5,5'-tetramethyl-4,4'-dibutyldipyrrolylmethene-2,2' (A), and 2,8,12,18-tetramethyl-3,7,13,17-tetrabutylporphin in various organic solvents were used to calculate the enthalpies of transfer Δtr H o from benzene and estimate the contribution of specific solvation caused by the additional coordination (Δc H o) of electron donor solvent molecules (pyridine and dimethylformamide). The greatest degree of coordination unsaturation and ability to extracoordination was characteristic of copper(II) and mercury(II) complexes with ligand A. The influence of the nature of the complex-forming metal, differences in the alkylation of the ligands, solvent properties, and the macrocyclization effect on the solvation and coordination unsaturation of metal complexes was discussed.

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