Dynamic Release–Immobilization of a Homogeneous Rhodium Hydroformylation Catalyst by a Polyoxometalate Metal–Organic Framework Composite

Thermal treatment of phosphotungstic acid (PTA)‐MIL‐101(Cr) composites in the presence of hydroformylation catalyst RhH(CO)(PPh3)3 leads to immobilization of the homogeneous Rh complex within the metal–organic framework (MOF) scaffold by coordination of PTA‐Rh. The Rh complex‐containing MOFs are tested in the hydroformylation of 1‐octene in which PTA competes with CO during ligand association. In the presence of the carbonyl ligand, the Rh complex is released from the MOF and behaves as a homogeneous catalyst. Therefore, the product spectra and selectivities of the Rh complex‐containing MOFs are similar to those of RhH(CO)(PPh3)3. Upon CO evacuation, Rh recoordinates to PTA, allowing for easy recycling of this new pseudo‐heterogeneous catalyst.

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