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

我们已经开发了一种新的四齿配体（Hdpfam）含有氮和磷的供体原子。该配体可合成多种双核配合物(M_2Ar_2（η-X)(η-dpfam)， M=Pd, Pt, Rh）。研究了利用仅由双核体系介导的双核配合物进行催化反应的发展，得到了以下结果：用硼氢化钠处理氯桥联铂双核配合物得到的双核铂氢化配合物Pt_2Tbl_2(η-H)（η-dpfam）是烷基硅氢化反应的良好催化剂。双核钯配合物对芳香族化合物C-H键的活化双核钯配合物对炔烃的氢化反应有活性，激活了通常被认为是惰性的芳环的C-H键。对反应机理的分析表明，反应是由钯中心直接激活C-H键进行的。烯烃C-H键的活化双核钯配合物对炔烃的氢烯化反应有活性，激活了通常被认为是惰性的烯烃双键的C-H键。双核钯配合物催化Suzuki-Miyaura反应，在苯溶剂中得到与正常产物相结合的产物。双核钯配合物催化双羰基化研究发现，双核钯配合物是碘苯与二乙胺双羰基化反应的活性催化剂。

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.