Ultralow‐Loading and High‐Performing Ionic Liquid‐Immobilizing Rhodium Single‐Atom Catalysts for Hydroformylation

We have developed a Keggin polyoxometalate (POM)‐based ionic‐liquid (IL)‐immobilizing rhodium single‐atom Rh catalyst (MTOA)5[SiW11O39Rh] (MOTA=methyltrioctylammonium cation) that can afford exceptionally high catalytic activity for the hydroformylation of alkenes to produce aldehydes at an ultralow loading of Rh (ca. 3 ppm). For styrene hydroformylation, both the conversion and the yield of the aldehyde can reach almost 99 %, and a TOF as high as 9000 h−1 was obtained without using any phosphine ligand in the reaction process. Further characterization by FTIR, ICP and ESI‐MS analysis revealed that the single Rh atom was incorporated in the lacunary POM anions. In particular, the bulky IL cation can play an additional role in stabilizing Rh species and thus prevent aggregation and leaching of Rh species. The IL catalyst was miscible with n‐hexane at temperatures; this contributed to exceptionally high activity for hydroformylation even at ultra‐low loading of IL catalyst. A keggin polyoxometalate (POM)‐based ionic liquid immobilizing rhodium single‐atom Rh catalyst exhibits an outstanding catalytic activity for styrene hydroformylation; both the conversion and the yield of aldehyde can reach almost 99 %, and a TOF was obtained as high as 9000 h−1 without using any phosphine ligand in the reaction process.