Heterogeneous Epoxide Carbonylation by Cooperative Ion-Pair Catalysis in Co(CO)(4)(–)-Incorporated Cr-MIL-101

[Image: see text] Despite the commercial desirability of epoxide carbonylation to β-lactones, the reliance of this process on homogeneous catalysts makes its industrial application challenging. Here we report the preparation and use of a Co(CO)(4)(–)-incorporated Cr-MIL-101 (Co(CO)(4)⊂Cr-MIL-101, Cr-MIL-101 = Cr(3)O(BDC)(3)F, H(2)BDC = 1,4-benzenedicarboxylic acid) heterogeneous catalyst for the ring-expansion carbonylation of epoxides, whose activity, selectivity, and substrate scope are on par with those of the reported homogeneous catalysts. We ascribe the observed performance to the unique cooperativity between the postsynthetically introduced Co(CO)(4)(–) and the site-isolated Lewis acidic Cr(III) centers in the metal–organic framework (MOF). The heterogeneous nature of Co(CO)(4)⊂Cr-MIL-101 allows the first demonstration of gas-phase continuous-flow production of β-lactones from epoxides, attesting to the potential applicability of the heterogeneous epoxide carbonylation strategy.