Heterogeneous epoxide carbonylation by cooperative ion-pair catalysis in Co(CO)4–-incorporated Cr-MIL-101

doi:10.1021/acscentsci.7b00075

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:

^[1];

^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Publication Date:: 2017-03-21

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.

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                    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.

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                    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.

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@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}

}

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DOI: 10.1021/acscentsci.7b00075

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

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Similar Records

Title: Heterogeneous epoxide carbonylation by cooperative ion-pair catalysis in Co(CO) 4 –-incorporated Cr-MIL-101

Abstract

Citation Formats

Recent Advances of MOFs and MOF-Derived Materials in Thermally Driven Organic Transformations journal, November 2018

Reactions of dicobalt octacarbonyl with dinucleating and mononucleating bis(imino)pyridine ligands journal, January 2018

Title: Heterogeneous epoxide carbonylation by cooperative ion-pair catalysis in Co(CO) ₄ ^–-incorporated Cr-MIL-101

Recent Advances of MOFs and MOF-Derived Materials in Thermally Driven Organic Transformations
journal, November 2018

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journal, January 2018