Abstract

The hydroformylation of olefins in supported room temperature liquid metals was developed, and the supported Rh liquid metal catalysts (Rh SLMCs) showed unprecedented activity and high selectivity for the hydroformylation of olefins to aldehydes. The turnover frequency is up to 7000 h−1, much higher than that of homogeneous RhCl3 + 3PPh3 catalyst. Moreover, the Rh SLMCs can be recovered conveniently without obvious deactivation, and the total turnover number is up to 250 000. The active Rh(I) catalyst formed in situ can be reduced back to Rh(0) by the free electrons in liquid metal when H2/CO gas is emitted, and thus Rh is not leaked into the organic solvent. Long‐chain olefins, cycloolefins and styrenes were applied, and the corresponding aldehydes were obtained in good to excellent yields.

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