Selective Oxidation with Aqueous Hydrogen Peroxide by [PO 4 {WO(O 2 ) 2 } 4 ] 3− Supported on Zinc‐Modified Tin Dioxide

We prepared supported phosphorus‐containing tetranuclear peroxotungstate ([PO 4 {WO(O 2 ) 2 } 4 ] 3− , denoted by PW4) catalysts by using zinc‐modified SnO 2 supports with different zinc contents [PW4‐Zn( x )/SnO 2 , in which x denotes the zinc content (wt %)]. The supported catalysts, in particular PW4‐Zn(0.8)/SnO 2 , could act as efficient and reusable heterogeneous catalysts for selective oxidation with aqueous H 2 O 2 as the terminal oxidant. The catalytic performance of PW4‐Zn(0.8)/SnO 2 was much superior to those of the corresponding homogeneous analogue THA 3 PW4 (THA=tetra‐ n ‐hexylammonium) and the previously reported tungstate‐based heterogeneous catalysts such as our W‐Zn/SnO 2 . In the presence of PW4‐Zn(0.8)/SnO 2 , various types of organic substrates such as alkenes, amines, silanes, and sulfides could be converted into the corresponding oxygenated products in high to excellent yields by using near‐stoichiometric amounts of H 2 O 2 with respect to the substrates (typically 1.2 equiv.). The PW4 species interacting with highly dispersed Zn 2+ species on SnO 2 likely plays an important role in the present oxidation.