Catalytic conversion of ethene to butadiene or hydrogenation to ethane on HY zeolite-supported rhodium complexes: Cooperative support/Rh-center route.

Rh(C₂H₄)₂ species grafted on the HY zeolite framework significantly enhance the activation of H₂ that reacts with C₂H₄ ligands to form C₂H₆. While in this case, the simultaneous activation of C₂H₄ and H₂ and the reaction between these species on zeolite-loaded Rh cations is a legitimate hydrogenation pathway yielding C₂H₆, the results obtained for Rh(CO)(C₂H₄)/HY materials exposed to H₂ convincingly show that the support-assisted C₂H₄ hydrogenation pathway also exists. This additional and previously unrecognized hydrogenation pathway couples with the conversion of C₂H₄ ligands on Rh sites and contributes significantly to the overall hydrogenation activity. This pathway does not require simultaneous activation of reactants on the same metal center and, therefore, is mechanistically different from hydrogenation chemistry exhibited by molecular organometallic complexes. We also demonstrate that the conversion of zeolite-supported Rh(CO)₂ complexes into Rh(CO)(C₂H₄) species under ambient conditions is not a simple CO/C₂H₄ ligand exchange reaction on Rh sites, as this process also involves the conversion of C₂H₄ into C₄ hydrocarbons, among which 1,3-butadiene is the main product formed with the initial selectivity exceeding 98% and the turnover frequency of 8.9 × 10^-3 s^-1. Thus, the primary role of zeolite-supported Rh species is not limited to the activation of H₂, as these species significantly accelerate the formation of the C₄ hydrocarbons from C₂H₄ even without the presence of H₂ in the feed. Using periodic density functional theory calculations, we examined several catalytic pathways that can lead to the conversion of C₂H₄ into 1,3-butadiene over these materials and identified the reaction route via intermediate formation of rhodacyclopentane.