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本文研究了配位俘获法固载胶体钯催化剂对Heck反应的催化行为,证明了碘苯与胶体钯之间的氧化加成反应引起催化剂颜色及钯的价态变化,钯金属键断裂,生成小分子钯化合物,并为含硫原子高分子配体俘获,进而参加一系列的催化循环。小分子钯化合物的生成,引起胶体催化剂的金属流失,而采用对钯有强配位能力的含硫原子配体,是该催化剂表现出较好稳定性的原因。讨论了影响Heck反应诱导期的各种因素,首次研究了加入三丁基碘化铵,磺对Heck反应诱导期的影响,极大地缩短了诱导期。
In this paper, the catalysis of colloidal palladium on immobilized colloidal palladium catalyst for Heck reaction was studied. It was proved that the oxidation reaction between iodobenzene and colloidal palladium caused the change of valence of catalyst color and palladium, the rupture of palladium metal bond and the formation of small Molecular palladium compounds, and sulfur atom-containing polymer ligand capture, and then participate in a series of catalytic cycles. The formation of small-molecule palladium compounds leads to the loss of metal from the colloidal catalyst. The use of sulfur atom-containing ligands with strong coordination ability to palladium is responsible for the better stability of the catalyst. The factors affecting the induction period of Heck reaction were discussed. The effect of adding tributyl ammonium iodide and sulfosulfate on the induction period of Heck reaction was studied for the first time, which greatly shortened the induction period.