Mechanistic Insights into Molecular Crystalline Organometallic Heterogeneous Catalysis through Parahydrogen-Based...

The heterogeneous solid-gas reactions of crystals of [Rh(L₂)(propene)][BAr^F₄] (1, L₂ = Bu₂PCH₂CH₂PBu₂) with H₂ 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-H₂ transfer, speciation changes in the crystalline catalyst at the molecular level, and allows for high-quality single-scan ¹H, ¹³C NMR gas-phase spectra for the products to be obtained, as well as 2D-measurements. Complex 1 reacts with H₂ to form dimeric [Rh(L₂)(H)(μ-H)]₂[BAr^F₄]₂ (4), as probed using EXAFS; meanwhile, a single-crystal of 1 equilibrates NMR silent para-H₂ with its NMR active ortho isomer, contemporaneously converting into 4, and 1 and 4 each convert para-H₂ into ortho-H₂ at different rates. Hydrogenation of propene using 1 and para-H₂ 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(Bu₂PCH₂CH₂PBu₂)(1,3,4-Me₃C₆H₃)][BAr^F₄], while with 1-butyne, rapid isomerization of 1-butyne occurs to give a butadiene complex, which then reacts with H₂ more slowly to form catalytically active 4. Surprisingly, the high PHIP hydrogenation efficiencies allow hyperpolarization effects to be seen when H₂ is taken directly from a regular cylinder at 25 °C. Finally, changing the chelating phosphine to Cy₂PCH₂CH₂PCy₂ results in initial high polarization efficiencies for propene hydrogenation, but rapid quenching of the catalyst competes to form the zwitterion [Rh(Cy₂PCH₂CH₂PCy₂){η⁶-(CF₃)₂(C₆H₃)}BAr^F₃].