Abstract
Molecularly defined organometallic rhodium phos-phine complexes were efficiently heterogenized within a MOF structure without affecting neither their molecular nature nor their catalytic behavior. Phosphine-functionalized MOF-808 served as a solid ligand in a series of eight rhodium phosphine catalysts. These MOF-heterogenized molecular catalysts showed activity up to 2100 h-1 for ethylene ...
Abstract
Molecularly defined organometallic rhodium phos-phine complexes were efficiently heterogenized within a MOF structure without affecting neither their molecular nature nor their catalytic behavior. Phosphine-functionalized MOF-808 served as a solid ligand in a series of eight rhodium phosphine catalysts. These MOF-heterogenized molecular catalysts showed activity up to 2100 h-1 for ethylene hydroformylation toward propionaldehyde as the sole carbon-containing product. The combined experimental and computational methods applied to this unique MOF-based molecular system allowed unraveling the structure and evolution of the active Rh species within the MOF under catalytic conditions, in line with the molecular mechanisms at play during the hydroformylation reaction. The MOF-based Rh catalyst also successfully catalyzed the hydroformylation of longer and bulkier alkenes with similar activity and selectivity than that obtained with its molecular homogeneous counterpart. MOF-808, designed as a porous crystalline macroligand for well-defined molecular catalysts, allows benefiting from the molecular scale understanding of interactions and mechanisms as well as from stabilization through site isolation and recycling ability.
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