Abstract
We have synthesized the compound meso-tetra(4-pyridyl)porphyrinatothallium (III) acetate, Tl(tpyp)(OAc), by using a new procedure, and characterized its structure through 1H/ 13C NMR spectroscopy, elemental analysis and the FABMS technique. The free energy of activation Δ G ‡ 233 for the acetato group exchange between Tl(tpyp)(OAc) and acetic acid in CD 2Cl 2 solvent has been derived to be 41.6±0.3 kJ mol −1 through 1H NMR temperature-dependent measurements. The Correlation Spectroscopy via Long-Range Coupling technique (COLOC) was used to resolve two quaternary carbons, i.e. C α and C −1 of Tl(tpyp)(OAc) at 149.6 and 149.8 ppm, respectively, at 21°C. In the slow exchange region, the methyl and carbonyl carbons of the acetato group are separately located at 17.6 ppm [with 3 J (Tl— 13C) coupling constant 314 Hz] and 174.1 ppm [with 2 J (Tl— 13C) coupling constant 256 Hz], for the Tl(tpyp)(OAc) case, and at 21.3 and 178.4 ppm for the HOAc case.
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