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Title: 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 = 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.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (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) (SC-22)
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 Volume: 3; Journal Issue: 5; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

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., 2017. 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. 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 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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acscentsci.7b00075

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Cited by: 6 works
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Works referencing / citing this record:

Recent Advances of MOFs and MOF-Derived Materials in Thermally Driven Organic Transformations
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Reactions of dicobalt octacarbonyl with dinucleating and mononucleating bis(imino)pyridine ligands
journal, January 2018

  • Hollingsworth, Ryan L.; Beattie, Jeffrey W.; Grass, Amanda
  • Dalton Transactions, Vol. 47, Issue 43
  • DOI: 10.1039/c8dt03405b