Hydroformylation and tandem isomerization-hydroformylation of n-decenes using a rhodium-BiPhePhos catalyst: Kinetic modeling, reaction network analysis and optimal reaction control

- Experimental hydroformylation reaction network analysis.
- Mechanistic kinetic modeling of the hydroformylation of n-decenes.
- Hydroformylation and tandem isomerization-hydroformylation of n-decene.
- Development of optimal reaction control strategies.

The rhodium-BiPhePhos catalyzed hydroformylation of n-decenes, as representative long-chain olefins, was investigated in this study experimentally and theoretically. Besides hydroformylation activity, the used catalyst enables significant double bond isomerization which is an essential side reaction. Because of this property, highly selective tandem isomerization-hydroformylation reactions that convert mixtures of n-decenes with internal double bond position to the desired terminal aldehyde undecanal are possible using the Rh-BiPhePhos catalyst. Experimentally, a reaction network analysis strategy was applied to study the coupled main and side reactions separately. Subsequently, a mechanistic kinetic model based on an extended Wilkinson-mechanism was developed that includes all relevant main and side reactions. Fitting the model to the 23 well planned experiments was possible with low deviations between model and experiment, including the tandem reaction. It was found that the tandem reaction shows completely opposite dependencies regarding temperature and synthesis gas pressure compared to the conventional hydroformylation of 1-decene, which is also covered by the model. Hence, strategies for optimal reaction performance of the (tandem isomerization-) hydroformylation were developed and presented.