Rhodium-BiPhePhos catalyzed hydroformylation studied by operando FTIR spectroscopy: Catalyst activation and rate determining step

Andreas Jörke , Andreas Seidel-Morgenstern , Christof Hamel
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引用次数: 17

Abstract

The homogeneously rhodium catalyzed hydroformylation of 1-decene was studied using operando FTIR spectroscopy. The bulky chelating diphosphite ligand BiPhePhos was used for catalyst modification. Special emphasis was given to the transformation of the Rh-precursor Rh(acac)(CO)2 to the activated HRh(BiPhePhos)(CO)2 catalyst. Under hydroformylation conditions, this complex was found to be the most abundant catalyst species over a wide range of olefin conversion. Other inactive or non-selective rhodium species were not detectable. Analysis of the turnover frequency revealed a first order dependence of the hydroformylation rate with respect to the concentration of 1-decene. These findings indicate that the coordination of the olefin to the Rh-BiPhePhos catalyst is determining the hydroformylation rate of 1-decene.

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用operando FTIR光谱研究了铑- biphephos催化的氢甲酰化反应:催化剂活化和速率测定步骤
利用operando FTIR光谱研究了均相铑催化的1-癸烯氢甲酰化反应。采用体积较大的螯合二亚磷酸酯配体BiPhePhos进行催化剂改性。特别强调了Rh前体Rh(acac)(CO)2转化为活化的HRh(BiPhePhos)(CO)2催化剂。在氢甲酰化条件下,该络合物被发现是在广泛的烯烃转化中最丰富的催化剂种类。其他非活性或非选择性铑未检出。对转换频率的分析揭示了氢甲酰化速率与1-癸烯浓度的一级依赖性。这些结果表明,烯烃与Rh-BiPhePhos催化剂的配位决定了1-癸烯的氢甲酰化速率。
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期刊介绍: The Journal of Molecular Catalysis A: Chemical publishes original, rigorous, and scholarly full papers that examine the molecular and atomic aspects of catalytic activation and reaction mechanisms in homogeneous catalysis, heterogeneous catalysis (including supported organometallic catalysis), and computational catalysis.
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