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

Chemistry. 2020 Nov 20;26(65):14896-14902. doi: 10.1002/chem.202001468. Epub 2020 Oct 15.

Abstract

The crown-shaped 36-molybdate cluster organophosphonate-functionalized polyoxomolybdates with the highest nuclearity in organophosphonate-based polyoxometalate chemistry, (NH4 )19 Na7 H10 [Cu(H2 O)TeMo6 O21 {N(CH2 PO3 )3 }]6 ⋅31 H2 O, 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.

Keywords: cage compounds; catalysis; organophosphonates; oxidation; polyoxometalates.