Tetrakis(thiadiazolo)porphyrazines. 3. Acid-base Properties and stability of tetrakis-3,4-(1,2,5-thiadiazolo)-porphyrazine in silfuric acid solutions

Autor: Irina A. Popkova, E. A. Pozdysheva, Pavel A. Stuzhin, O. V. Mal’chugina, Claudio Ercolani
Rok vydání: 2005
Předmět:
Popis: AM1 calculations gave the proton affinities of different types of donor sites in tetrakis-3,4-(1,2,5-thiadiazolo)porphyrazine, H2{[SN2)4PA}, and protonation of the meso-nitrogen atoms was found to be favored. A spectrometric study showed that the basicity of the meso-nitrogen atoms of the porphyrazine macrocycle is strongly diminished and these atoms in CF3CO2H are involved in an incomplete acid-base interaction (ABI) to give acid solvates, while a complete ABI (protonation) is found only in the presence of sulfuric acid. The basicity constants of the meso-nitrogen atoms were determined spectrophotometrically in CF3CO2H-H2SO4. The kinetics of decomposition of the macrocyclic chromophore in concentrated sulfuric acid was studied and a possible mechanism for this process was proposed.
Databáze: OpenAIRE