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The combination of parahydrogen induced polarization (PHIP), kinetics and NMR spectroscopy yields a powerful analytical tool: quantitative in situ NMR spectroscopy. Two versions of PHIP NMR experiments are presented to investigate the kinetics of homogeneously catalyzed hydrogenations. The first method, an experimental variation of the ROCHESTER experiment (ROCHESTER = rates of catalytic hydrogenation estimated spectroscopically through enhanced resonances), allows one to determine the hydrogenation rate independently of relaxation and other sources of decay, e.g., subsequent chemical reaction steps. The second method named DYPAS (dynamic PASADENA spectroscopy) uses a variable delay between the end of the hydrogen-addition period and the detection pulse. In principle, all processes during this delay can be described by a set of coupled differential equations. Their solutions can be fitted to the experimental data by a least-squares optimization of the involved kinetic parameters. The DYPAS method can be used to determine the rates of formation as well as the rates of decomposition of stable intermediates and has been applied to the case of freshly hydrogenated and still catalyst-attached product molecules. We provide kinetic data for the formation and decomposition of these unusual product-catalyst complexes during the hydrogenation of different styrene derivatives with a cationic RhI catalyst containing a chelating diphosphine ligand. The kinetic measurements indicate that the rate of formation of the catalyst-attached product increases whereas the rate constant of its decomposition diminishes if the para position of the arene ring of styrene carries an electron-donating substituent. In the case of p-aminostyrene as the substrate, the detachment step turned out to be rate limiting for the catalytic cycle. With certain substituted styrenes and cationic RhI complexes containing chiral chelating diphosphine ligands, two geometrically different (diastereomeric) product-catalyst adducts can be discriminated via PHIP NMR spectroscopy. The associated alternative reaction pathways have been analyzed by applying the DYPAS method, which can also be used to investigate the mechanism of an asymmetric hydrogenation
