Phosphine metal–organic frameworks (P-MOFs) are an emerging class of coordination polymers that provide novel opportunities for metal–supported catalysis as solid ligands. Here, we present the synthesis and characterization of three novel P-MOFs based on a (diphenylphosphino)­terephthalic acid linker. We targeted the structures of MOF-5, MIL-101­(Cr), and MIL-101­(Al)-NH2 to produce materials with partial diphenylphosphine substitution, which were crystalline and highly porous.

Metal–organic frameworks (MOFs) are ideal hosts for incorporation of molecular complexes without altering their original ligand environment; molecular catalysts can thus be easily synthesized and used in gas- and vapor-phase reactions operated in continuous mode. We report the immobilization of a molecular ruthenium complex in a phosphine-functionalized MOF that is highly efficient in the vapor-phase dehydrogenation of formic acid. The catalyst exhibited exclusive selectivity to hydrogen and carbon dioxide with outstanding stability at 145 °C (TON > 1 290 000). Our results represent a noteworthy improvement over heterogeneous ruthenium systems in terms of selectivity in the gas-phase, while reaching a productivity level higher than that of state-of-the-art homogeneous catalysts.