Molecular Design of Polyoxometalate-Based Compounds for Environmentally-Friendly Functional Group Transformations: From Molecular Catalysts to Heterogeneous Catalysts

作者：Mizuno Noritaka^*; Yamaguchi Kazuya; Kamata Keigo

来源：Catalysis Surveys from Asia, 2011, 15(2): 68-79.

DOI：10.1007/s10563-011-9111-2

• Polyoxometalate
• Molecular design Controlled active sites
• Molecular heterogeneous catalysts
• Environmentally-friendly functional group transformations

This review article summarizes our recent researches for molecular design of polyoxometalates (POMs) and their related compounds for environmentally-friendly functional group transformations. The divacant POM [gamma-SiW(10)O(34)(H(2)O)(2)](4-) exhibits high catalytic performance for mono-oxygenation-type reactions including epoxidation of olefins and allylic alcohols, sulfoxidation, and hydroxylation of organosilanes with H(2)O(2). We have successfully synthesized several POM-based molecular catalysts (metal-substituted POMs) with controlled active sites by the introduction of metal species into the divacant POM as a "structural motif". These molecular catalysts can efficiently activate H(2)O(2) (vanadium-substituted POM for epoxidation) and alkynes (copper-substituted POM for click reaction and oxidative homocoupling of alkynes). The aluminum-substituted POM exhibits Lewis acidic catalysis for diastereoselective cyclization of (+)-citronellal to (-)-isopulegol. In addition, we have developed POM-based "molecular heterogeneous catalysts" by the "solidification" and "immobilization" of catalytically active POMs.

• 出版日期2011-6