Hybrid Materials Based on Imidazo[4,5-b]porphyrins for Catalytic Oxidation of Sulfides

Heterogenized metalloporphyrin catalysts for oxidation reactions are extensively explored to improve chemical production. In this work, manganese meso-tetraarylporphyrins were immobilized on hydrated mesoporous titanium dioxide (S-BET = 705 m(2) g(-1)) through carboxylate or phosphonate anchoring groups separated from the macrocycle by the 2-arylimidazole linker fused across one of the pyrrolic rings of the macrocycle. The element composition of two mesoporous hybrid materials thus obtained were investigated and the integrity of the immobilized complexes was shown by different physicochemical methods. Finally, the catalytic efficiency of the more stable material Mn(TMPIP)/TiO2 with the phosphonate anchor was evaluated in the selective oxidation of sulfides to sulfoxides by molecular oxygen in the presence of isobutyraldehyde (IBA). The heterogenized complex has shown excellent catalytic activity exhibiting a turnover (TON) of similar to 1100 in a single catalytic run of the sulfoxidation of thioanisole. The catalyst was successfully reused in seven consecutive catalytic cycles.

Automated summary

Heterogenized metalloporphyrin catalysts were immobilized on hydrated mesoporous titanium dioxide through carboxylate or phosphonate anchoring groups. The element composition of the obtained mesoporous materials was investigated and the integrity of the immobilized complexes was confirmed. The catalytic efficiency of the more stable material Mn(TMPIP)/TiO2 with the phosphonate anchor was evaluated in the selective oxidation of sulfides to sulfoxides, showing excellent catalytic activity.