Generating parahydrogen-induced polarization using immobilized iridium complexes in the gas-phase hydrogenation of carbon-carbon double and triple bonds

Abstract

Immobilized iridium complexes synthesized using [Ir(COD)Cl]2 by anchoring on hydrous and anhydrous silica gels were studied in terms of generating parahydrogen-induced polarization (PHIP) in the gas-phase hydrogenation of propylene and propyne. Distinguishing differences in the hydrogenations of carbon– carbon double and triple bonds were found. It has been shown that in the double bond hydrogenation both catalysts are very active even at 25 C. The reaction yield in continuous flow experiments is more than 70 %, whereas the obtained PHIP degrees are very low. In the case of the triple bond hydrogenation, a more or less active hydrogenation reaction was observed at relatively high temperatures (&70–80 C) for the catalyst immobilized on anhydrous silica, while the catalyst immobilized on hydrous silica was inactive at these temperatures. Contrary to the double bond hydrogenation, the triple bond hydrogenation provided significant signal enhancements observed in 1H nuclear magnetic resonance spectra for the signals corresponding to protons of vinyl fragments of product propylene in both PASADENA and ALTADENA experiments. The catalyst, however, is not stable under the triple bond hydrogenation reaction conditions, and deactivates within several minutes. It was also found that at higher temperatures (100–120 C), this catalyst demonstrates a reactivation most likely associated with the reduction of Ir(I) that results in the formation of Ir(0) surface metal nanoparticles.