Copper-Containing Polyoxometalate-Based Metal-Organic Framework as a Catalyst for the Oxidation of Silanes: Effective Cooperative Catalysis by Metal Sites and POM Precursor.

The oxidation of silanes into silanols is a very necessary transformation, and yet the rational fabrication of efficient catalysts for this reaction remains a challenging task. Here, a 3D polyoxometalate-based metal-organic framework (POMOF), [Cu Ι 3 (pz) 3 {PMo 12 O 40 }]·H 2 O ( HENU-8 , HENU = Henan University; pz = pyrazine) was consciously prepared and first employed in the oxidation of dimethylphenylsilane with tert -butyl hydroperoxide (TBHP) as an oxidant, achieving 89% yield at a production rate of 132 mmol·g -1 ·h -1 . Control experiments indicated that polyoxometalates and Cu atoms together affected the ultimate outcome in this catalytic system, and the designed catalyst followed a free radical mechanism.