Heterogeneous epoxide carbonylation by cooperative ion-pair catalysis in Co(CO) 4 –-incorporated Cr-MIL-101
Here, 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) 4cCr-MIL-101, Cr-MIL-101 = Cr 3O(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) 4cCr-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.
[1]- Publication Date:
- Grant/Contract Number:
- SC0016214
- Type:
- Published Article
- Journal Name:
- ACS Central Science
- Additional Journal Information:
- Journal Volume: 3; Journal Issue: 5; Journal ID: ISSN 2374-7943
- Publisher:
- American Chemical Society (ACS)
- Research Org:
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Sponsoring Org:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
- OSTI Identifier:
- 1348018
- Alternate Identifier(s):
- OSTI ID: 1369461
Park, Hoyoung D., Dinca, Mircea, and Roman-Leshkov, Yuriy. Heterogeneous epoxide carbonylation by cooperative ion-pair catalysis in Co(CO)4–-incorporated Cr-MIL-101. United States: N. p.,
Web. doi:10.1021/acscentsci.7b00075.
Park, Hoyoung D., Dinca, Mircea, & Roman-Leshkov, Yuriy. Heterogeneous epoxide carbonylation by cooperative ion-pair catalysis in Co(CO)4–-incorporated Cr-MIL-101. United States. doi:10.1021/acscentsci.7b00075.
Park, Hoyoung D., Dinca, Mircea, and Roman-Leshkov, Yuriy. 2017.
"Heterogeneous epoxide carbonylation by cooperative ion-pair catalysis in Co(CO)4–-incorporated Cr-MIL-101". United States.
doi:10.1021/acscentsci.7b00075.
@article{osti_1348018,
title = {Heterogeneous epoxide carbonylation by cooperative ion-pair catalysis in Co(CO)4–-incorporated Cr-MIL-101},
author = {Park, Hoyoung D. and Dinca, Mircea and Roman-Leshkov, Yuriy},
abstractNote = {Here, 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)4cCr-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)4cCr-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.},
doi = {10.1021/acscentsci.7b00075},
journal = {ACS Central Science},
number = 5,
volume = 3,
place = {United States},
year = {2017},
month = {3}
}