36‐Nuclearity Organophosphonate‐Functionalized Polyoxomolybdates: Synthesis, Characterization and Selective Catalytic Oxidation of Sulfides

Abstract The crown‐shaped 36‐molybdate cluster organophosphonate‐functionalized polyoxomolybdates with the highest nuclearity in organophosphonate‐based polyoxometalate chemistry, (NH4)19Na7H10[Cu(H2O)TeMo6O21{N(CH2PO3)3}]6⋅31 H2O, has been reported for the first time. The synthesized 36‐molybdate cluster was characterized by routine techniques and tested as a heterogeneous catalyst for selective oxidation of sulfides with impressive catalytic and selective performances after heat treatment. High efficiency (TON=15333) was achieved in the selective oxidation of sulfides to sulfoxides, caused by the synergic effect between copper and polyoxomolybdates and the generation of the cuprous species during the heat treatment.