Heterogeneous Epoxide Carbonylation by Cooperative Ion-Pair Catalysis in Co(CO) 4 – -Incorporated Cr-MIL-101
Abstract
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.
- Authors:
-
- Department of Chemical Engineering and ‡Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
- Publication Date:
- Research Org.:
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1348018
- Alternate Identifier(s):
- OSTI ID: 1369461
- Grant/Contract Number:
- SC0016214
- Resource Type:
- Published Article
- Journal Name:
- ACS Central Science
- Additional Journal Information:
- Journal Name: ACS Central Science Journal Volume: 3 Journal Issue: 5; Journal ID: ISSN 2374-7943
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Park, Hoyoung D., Dincă, Mircea, and Román-Leshkov, Yuriy. Heterogeneous Epoxide Carbonylation by Cooperative Ion-Pair Catalysis in Co(CO) 4 – -Incorporated Cr-MIL-101. United States: N. p., 2017.
Web. doi:10.1021/acscentsci.7b00075.
Park, Hoyoung D., Dincă, Mircea, & Román-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., Dincă, Mircea, and Román-Leshkov, Yuriy. Tue .
"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 Dincă, Mircea and Román-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}
}
DOI: 10.1021/acscentsci.7b00075
Web of Science
Works referencing / citing this record:
Recent Advances of MOFs and MOF-Derived Materials in Thermally Driven Organic Transformations
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- Yang, Shuliang; Peng, Li; Bulut, Safak
- Chemistry - A European Journal, Vol. 25, Issue 9
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- Hollingsworth, Ryan L.; Beattie, Jeffrey W.; Grass, Amanda
- Dalton Transactions, Vol. 47, Issue 43
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- Yang, Shuliang; Peng, Li; Bulut, Safak
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- Dalton Transactions, Vol. 47, Issue 43
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- Tu, Wenguang; Xu, You; Yin, Shengming
- Advanced Materials, Vol. 30, Issue 33
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- Tan, Ying Chuan; Zeng, Hua Chun
- ChemCatChem, Vol. 11, Issue 14
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journal, August 2018
- Yang, Shuliang; Peng, Li; Sun, Daniel T.
- ChemSusChem, Vol. 11, Issue 18
Stable metal–organic frameworks as a host platform for catalysis and biomimetics
journal, January 2018
- Qin, Jun-Sheng; Yuan, Shuai; Lollar, Christina
- Chemical Communications, Vol. 54, Issue 34
An aluminum( iii ) picket fence phthalocyanine-based heterogeneous catalyst for ring-expansion carbonylation of epoxides
journal, January 2019
- Jiang, Jianwei; Yoon, Sungho
- Journal of Materials Chemistry A, Vol. 7, Issue 11