Spectrophotometric studies of the thermodynamics of sitting-atop complexation between free base meso-tetraarylporphyrins and titanium(IV) chloride

Abstract: Titanium(IV) chloride reacts with free base meso-tetraarylporphyrin and its ortho, meta and para-substituted derivatives (H2T(X)PP; X: OCH3, CH3 and Cl) for formation of sitting-atop (SAT) complexes, [TiCl4(H2T(X)PP)]. The computer fitting of the variation of the absorbance versus mole ratio by KINFIT program was used for calculation of the formation constants of these complexes in chloroform. Thermodynamic parameters, ΔG°, ΔH°, ΔS°, have been determined and the influence of the temperature and the substituted aryl groups (electronic and steric effects) in the free base porphyrins on the stability of the SAT complexes was studied. [Copyright &y& Elsevier]