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. 2017 May 24;3(5):444-448.
doi: 10.1021/acscentsci.7b00075. Epub 2017 Mar 21.

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

Hoyoung D Park  1 , Mircea Dincă  1 , Yuriy Román-Leshkov  1
Affiliations

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

Hoyoung D Park et al. ACS Cent Sci. .

Abstract

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 = Cr3O(BDC)3F, H2BDC = 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.

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Conflict of interest statement

The authors declare the following competing financial interest(s): The authors and MIT have filed a patent on some of the results herein.

Figures

Figure 1
Figure 1
(A) Proposed catalytic cycle for the ring-expansion carbonylation of epoxides by [Lewis acid]+[Co(CO)4]−. (B) Illustration of the structure of [(OEP)Cr(THF)2]+[Co(CO)4]− (OEP = 2,3,7,8,12,13,17,18-octaethylporphyrinato, THF = tetrahydrofuran). (C) Illustration of the structure of [(salph)Cr(THF)2]+[Co(CO)4]− (salph = N,N′-o-phenylenebis(3,5-di-tert-butylsalicylideneimine)). (D) Illustration of the metal cluster structure of Co(CO)4⊂Cr-MIL-101 with coordinated THF molecules.
Figure 2
Figure 2
(A) EDX spectra of Cr-MIL-101-F, Cr-MIL-101-Cl, and Co(CO)4⊂Cr-MIL-101. Au peaks from the preanalysis Au coating of samples. (B) ATR-IR absorption spectra of Cr-MIL-101-Cl and Co(CO)4⊂Cr-MIL-101.
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