摘要
丙烯Reppe反应制丁醇自1953年Reppe等人发现以来,催化剂主要是铁、钴、铑三体系,都前后分别实现了工业化生产。从反应工艺条件、催化剂的各项性能指标、原料资源等方面考虑,各有利弊。因此,深入研究各簇合物在此反应中的催化作用,开拓具有应用前景的新型催化剂,在实践和理论上都有重要的意义。我们考察了铁系在此反应中的催化性能,从动力学特征到红外光谱分析都发现了某些过去未曾报导的重要结果,证实了G.H.Olive等人的看法:铁系在丙烯Reppe反应中的催化作用机理从活性物种到动力学还要做更多的研究工作。
[ Et3NH]+ [ HFe3 ( CO )11]- was prepared from Fe ( CO ) 5, The molar catalytic activity of [HFe3 ( CO ) 11]- in the hydrohydroxyme-thylation of propene to butanol is five-fold higher than that of Fe ( CO ) 5, and the n/i ratio of butanols was 1.5 fold higher. The c'onversion of propene is 65%.
The IR spectra and kinetic charaterization showed that trinuclear and mononuclear iron anions co-existed in the reacting solution.They play different catalytic roles in the hydroformylation and hydrogena-tion. Due to the cooperation of trinuclear and mononuclear species, [ HFe3 ( CO )11]- presents high catalytic activity.
[HFe3(CO)11]- cluster was not deactivated by the deoxygenized water, but it was sensitive to O2 after deliquescence. It was first hydrolyzed to Fe3(CO)12 and FeCO3,and then oxidized to carbonate. [Et3NH]+ stabilized the trinuclear iron anion, but the presence of H2O makes the[HFe3(CO)11]- to lose the protection of Lewis acid and its decomposition by O2 was accelerated.
出处
《分子催化》
EI
CAS
CSCD
1991年第2期184-188,共5页
Journal of Molecular Catalysis(China)
基金
国家自然科学基金
