The kinetics of the hydroformylation of 3,3-dimethyl-1-butene with a rhodium monophosphite catalyst has been studied in detail. Time-dependent concentration profiles covering the entire olefin conversion range were derived from in situ high-pressure FTIR spectroscopic data for both, pure organic components and catalytic intermediates. These profiles fit to Michaelis-Menten-type kinetics with competitive and uncompetitive side reactions involved. The characteristics found for the influence of the hydrogen concentration verify that the pre-equilibrium towards the catalyst substrate complex is not established. It has been proven experimentally that the hydrogenolysis of the intermediate acyl complex remains rate limiting even at high conversions when the rhodium hydride is the predominant resting state and the reaction is nearly of first order with respect to the olefin. Results from in situ FTIR and high-pressure (HP) NMR spectroscopy and from DFT calculations support the coordination of only one phosphite ligand in the dominating intermediates and a preferred axial position of the phosphite in the electronically saturated, trigonal bipyramidal (tbp)-structured acyl rhodium complex.
Herein we report the evaluation of the frequently employed tetrabutyl ammonium and phosphonium halides as well as their bifunctional analogs as catalysts in cyclic carbonate synthesis under benchmarked conditions. The kinetic data of all catalysts were evaluated and the rate constants determined. Moreover, a systematic infrared spectroscopic study of the interactions between cation and anion of the catalysts as well as the interactions between the catalysts and the substrate were conducted. These experimental results were additionally supported by DFT calculations. The observed trends in the interaction between the onium cation and the anion are correlated to their catalytic activity. Moreover, these investigations revealed the mode of the substrate activation for the monofunctional and the bifunctional catalysts. Furthermore, the kinetic studies and in situ infrared experiments revealed a product inhibition of the bifunctional catalysts via the unexpected formation of catalyst−carbonate adducts. The interaction between the catalysts and the product was further studied by infrared spectroscopy. Finally, the rate and the equilibrium constants for the binfunctional catalysts were determined by a Michaelis− Menten model considering a reversible product inhibition.
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