Mechanistic Insights into Molecular Crystalline Organometallic Heterogeneous Catalysis through Parahydrogen-Based Nuclear Magnetic Resonance Studies

[Image: see text] The heterogeneous solid–gas reactions of crystals of [Rh(L(2))(propene)][BAr(F)(4)] (1, L(2) = (t)Bu(2)PCH(2)CH(2)P(t)Bu(2)) with H(2) and propene, 1-butene, propyne, or 1-butyne are explored by gas-phase nuclear magnetic resonance (NMR) spectroscopy under batch conditions at 25 °C. The temporal evolution of the resulting parahydrogen-induced polarization (PHIP) effects measures catalytic flux and thus interrogates the efficiency of catalytic pairwise para-H(2) transfer, speciation changes in the crystalline catalyst at the molecular level, and allows for high-quality single-scan (1)H, (13)C NMR gas-phase spectra for the products to be obtained, as well as 2D-measurements. Complex 1 reacts with H(2) to form dimeric [Rh(L(2))(H)(μ-H)](2)[BAr(F)(4)](2) (4), as probed using EXAFS; meanwhile, a single-crystal of 1 equilibrates NMR silent para-H(2) with its NMR active ortho isomer, contemporaneously converting into 4, and 1 and 4 each convert para-H(2) into ortho-H(2) at different rates. Hydrogenation of propene using 1 and para-H(2) results in very high initial polarization levels in propane (>85%). Strong PHIP was also detected in the hydrogenation products of 1-butene, propyne, and 1-butyne. With propyne, a competing cyclotrimerization deactivation process occurs to afford [Rh((t)Bu(2)PCH(2)CH(2)P(t)Bu(2))(1,3,4-Me(3)C(6)H(3))][BAr(F)(4)], while with 1-butyne, rapid isomerization of 1-butyne occurs to give a butadiene complex, which then reacts with H(2) more slowly to form catalytically active 4. Surprisingly, the high PHIP hydrogenation efficiencies allow hyperpolarization effects to be seen when H(2) is taken directly from a regular cylinder at 25 °C. Finally, changing the chelating phosphine to Cy(2)PCH(2)CH(2)PCy(2) results in initial high polarization efficiencies for propene hydrogenation, but rapid quenching of the catalyst competes to form the zwitterion [Rh(Cy(2)PCH(2)CH(2)PCy(2)){η(6)-(CF(3))(2)(C(6)H(3))}BAr(F)(3)].