Pairwise and random addition processes are ordinarily indistinguishable in hydrogenation reactions. The distinction becomes important only when the fate of spin correlation matters, such as in parahydrogen-induced polarization (PHIP). Supported metal catalysts were not expected to yield PHIP signals given the rapid diffusion of H atoms on the catalyst surface and in view of the sequential stepwise nature of the H atom addition in the Horiuti-Polanyi mechanism. Thus, it seems surprising that supported metal hydrogenation catalysts can yield detectable PHIP NMR signals. Even more remarkably, supported Pt and Ir nanoparticles are shown herein to catalyze pairwise replacement on propene and 3,3,3-trifluoropropene. By simply flowing a mixture of parahydrogen and alkene over the catalyst, the scalar symmetrization order of the former is incorporated into the latter without a change in molecular structure, producing intense PHIP NMR signals on the alkene. An important indicator of the mechanism of the pairwise replacement is its stereoselectivity, which is revealed with the aid of density matrix spectral simulations. PHIP by pairwise replacement has the potential to significantly diversify the substrates that can be hyperpolarized by PHIP for biomedical utilization.
Intense para-hydrogen-enhanced NMR signals are observed in the hydrogenation of propene and propyne over ceria nanocubes, nano-octahedra, and nanorods. The well-defined ceria shapes, synthesized by a hydrothermal method, expose different crystalline facets with various oxygen vacancy densities, which are known to play a role in hydrogenation and oxidation catalysis. While the catalytic activity of the hydrogenation of propene over ceria is strongly facet-dependent, the pairwise selectivity is low (2.4% at 375 °C), which is consistent with stepwise H atom transfer, and it is the same for all three nanocrystal shapes. Selective semi-hydrogenation of propyne over ceria nanocubes yields hyperpolarized propene with a similar pairwise selectivity of (2.7% at 300 °C), indicating product formation predominantly by a non-pairwise addition. Ceria is also shown to be an efficient pairwise replacement catalyst for propene.
Parahydrogen induced polarization using heterogeneous catalysis can produce impurity-free hyperpolarized gases and liquids, but the comparatively low signal enhancements and limited scope of substrates that can be polarized pose significant challenges to this approach. This study explores the surface processes affecting the disposition of the bilinear spin order derived from parahydrogen in the hydrogenation of propyne over TiO2-supported Pt nanoparticles. The hyperpolarized adducts formed at low magnetic field are adiabatically transported to high field for analysis by proton NMR spectroscopy at 400 MHz. For the first time, the stereoselectivity of pairwise addition to propyne is measured as a function of reaction conditions. The correlation between partial reduction selectivity and stereoselectivity of pairwise addition is revealed. The systematic trends are rationalized in terms of a hybrid mechanism incorporating non-traditional concerted addition steps and well-established reversible step-wise addition involving the formation of a surface bound 2-propyl intermediate.
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