Hybrid polyoxometalate palladacycles: DFT study and application to the Heck reaction

作者：Riflade Benoit; Oble Julie; Chenneberg Ludwig; Derat Etienne^*; Hasenknopf Bernold; Lacote Emmanuel; Thorimbert Serge

来源：Tetrahedron, 2013, 69(27-28): 5772-5779.

DOI：10.1016/j.tet.2013.03.045

• Hybrid polyoxometalate
• Catalysis
• Heck reaction
• C-H insertion
• Palladacycles

The phosphovanadotungstate polyanion [P2W15V3O62](9-) is a powerful support to stabilize palladacycles conjugated to the inorganic framework via an organic ligand. The insertion can be directed toward sp(2) or sp(3) C-H insertion upon appropriate choice of the substitution pattern on the organic ligand. OFT modeling indicates that the strong withdrawing effect of the POM transmitted through the conjugated carbonyl was responsible for this easy insertion. The palladacycles led to the formation of stilbene via a Mizoroki-Heck reaction. However it is likely that the POMs act as Pd-reservoirs for the formation of nanoparticles.

• 出版日期2013-7-8