Synthesis of novel transition metal dinuclear complex catalyst and application to organic synthesis

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We have exploited a novel tetradentate ligand (Hdpfam) containing nitrogen and phosphorus donor atoms. Several dinuclear complexes (M_2Ar_2(η-X)(η-dpfam), M=Pd, Pt, Rh) can be synthesized using this ligand. Development of catalytic reactions utilizing the dinuclear complexes mediated only by dinuclear system has been studied and the following results are obtained.1.Hydrosilylation of alkynes catalyzed by dinuclear platinum complexDinuclear platinum hydride complex Pt_2Tbl_2(η-H)(η-dpfam)) obtained by treatment of the chloride bridged platinum dinuclear complex with sodium borohydride was found to be a good catalyst for the hydrosilylation of alkynes.2.Activation of C-H bond of aromatic compounds by dinuclear palladium complexesDinuclear palladium complexes were found active far hydroarylation of alkynes activating the C-H bond of an aromatic ring which was usually regarded inert. Elucidation of the reaction mechanism uncovered that the reaction proceeds with direct C-H bond activation by palladium center.3.Activation of C-H bond of alkenesDinuclear palladium complexes were found active for hydroalkenylation of alkynes activating the C-H bond of an alkene double bond which was usually regarded inert.4.Suzuki-Miyaura reaction catalyzed by dinuclear palladium complexDinuclear palladium complexes catalyzed the Suzuki-miyaura reaction in benzene solvent to give a cine product together with the normal one.5.Double carbonylation catalyzed by dinuclear palladium complexDinuclear palladium complex was found to be an active catalyst for the double carbonylation of iodobenzene with diethylamine.