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以PdCl_2(PPh_3)_2-PPh_3为催化剂母体,醇为溶剂,烯烃的氢羧基化反应,Knifton分离出HPdCl(PPh_3)_2·SnCl_3;Bardi等得到trans-Pd(COPr-n)Cl(PPh_3)_2,认为此反应是氢化物机理,Carinato等用甲醇作溶剂,反应后得到trans-[Pd(COPr-n)Cl(pph-3)_2]和trans-[Pd(COOMe)Cl(pph_3)_2]两种配合物.提出反应经由Pd—H与Pd—CO_2R中间物有关的两条路径,Pd—CO_2R是由CO插入Pd—OR中形成的.至今,对该反应的机理仍有争议.本文用原位红外光谱法跟踪反应全过程,检测反应中的活性中间物,提出在合成气压力下钯-膦催化剂烯烃氢羧化的反应机理.
Pd-P (PPh_3) _2-PPh_3 was used as the precursor of the catalyst and alcohol was used as the solvent. Hydrocarboxylation of olefins was carried out. Knifton was used to separate HPdCl (PPh_3) _2 · SnCl_3 and Bardi et al. , The reaction was considered to be a hydride mechanism and Carinato et al. Used methanol as a solvent to obtain trans- [Pd (COPr-n) Cl (pph-3) _2] and trans- [Pd (COOMe) Cl (pph_3) _2] Two complexes, Pd-CO_2R and Pd-CO_2R, were introduced into Pd-OR via Pd-H and Pd-CO_2R, respectively. Up to now, the mechanism of this reaction remains controversial. In situ FT - IR spectroscopy was used to trace the whole process of the reaction and the active intermediates in the reaction were detected. The reaction mechanism of hydrogenation of olefins with palladium - phosphine catalyst under syngas pressure was proposed.