Abstract
The formation of Ga3+, In3+, and Tl3+ tetraphenylporphine mixed-ligand complexes (X)MTPP + L = (X)M(L)TPP (X = Cl-, AcO-, acac-; L = N-methylimidazole, imidazole, pyridine, 3,5-dimethylpyrazole, dimethylformamide) in chloroform was studied by spectrophotometric titration and quantum-chemical calculations. The stability of the Ga, In, and Tl porphyrin extra complexes was found to depend on the nature of the acido and nitrogen-containing ligands. The geometric and energetic characteristics of the complexes of six-coordinate gallium and indium porphyrins were calculated. Correlations between calculated and experimental energies of formation and Gibbs energies were found. The cis- and trans-effects of ligands in the extra complexes of metal porphyrins were explained.
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