Parahydrogen-Induced Polarization in Heterogeneous Hydrogenations over Silica-Immobilized Rh Complexes

The use of heterogeneous catalysts for parahydrogen-induced polarization (PHIP) of nuclear spins opens new horizons for production of hyperpolarized substances. Immobilization of homogeneous hydrogenation catalysts is a promising approach for designing the efficient heterogeneous catalytic systems capable of PHIP generation. Herein, we study the formation of PHIP in the gas-phase and in the liquid-phase hydrogenations of propyne and propylene catalyzed by silica-immobilized Rh complexes synthesized by the ligand-exchange anchoring of the Wilkinson's complex RhCl(PPh3)(3), the binuclear complex Rh2Cl2(C8H12)(2) and the cationic complex [Rh(C8H12)(2)](+)[BF4](-) to the phosphine-modified silica gel. We consider the stability and the mechanistic aspects of the hydrogenation over the immobilized Wilkinson's catalyst in terms of PHIP observation. Using a PASADENA (parahydrogen and synthesis allow dramatically enhanced nuclear alignment) effect, it is found, in particular, that liquid-phase propyne hydrogenation over the immobilized Wilkinsons's catalyst at 70 degrees C proceeds in a stable regime with a stereoselective cis addition of a hydrogen molecule, while in the gas phase at the same temperature the hydrogenation stereoselectivity is observed only for a short time after the reaction is started, and then the catalyst rapidly loses its activity. The reasons of the catalyst deactivation are discussed based on the literature data, the results of infrared spectroscopy study, and the comparison to the behavior of the immobilized binuclear and cationic Rh complexes. In addition, it is shown that the immobilized Wilkinson's catalyst is reduced as temperature increases in the range of 90-130 degrees C, as confirmed by X-ray photoelectron spectroscopy.