Anion-Receptor Mediated Oxidation of Carbon Monoxide to Carbonate by Peroxide Dianion

Nava, Matthew; Lopez, Nazario; Müller, Peter; Wu, Gang; Nocera, Daniel G.; Cummins, Christopher C.

doi:10.1021/jacs.5b08495

Title: Anion-Receptor Mediated Oxidation of Carbon Monoxide to Carbonate by Peroxide Dianion

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Abstract

The reactivity of peroxide dianion O₂^2– has been scarcely explored in organic media due to the lack of soluble sources of this reduced oxygen species. We now report the finding that the encapsulated peroxide cryptate, [O₂cmBDCA-5t-H₆]^2– (1), reacts with carbon monoxide in organic solvents at 40 °C to cleanly form an encapsulated carbonate. Characterization of the resulting hexacarboxamide carbonate cryptate by single crystal X-ray diffraction reveals that carbonate dianion forms nine complementary hydrogen bonds with the hexacarboxamide cryptand, [CO₃cmBDCA-5t-H₆]^2– (2), a conclusion that is supported by spectroscopic data. Labeling studies and ¹⁷O solid-state NMR data confirm that two-thirds of the oxygen atoms in the encapsulated carbonate derive from peroxide dianion, while the carbon is derived from CO. Further evidence for the formation of a carbonate cryptate was obtained by three methods of independent synthesis: treatment of (i) free cryptand with K₂CO₃; (ii) monodeprotonated cryptand with PPN[HCO₃]; and (iii) free cryptand with TBA[OH] and atmospheric CO₂. This work demonstrates CO oxidation mediated by a hydrogen-bonding anion receptor, constituting an alternative to transition-metal catalysis.

Authors:

Nava, Matthew ^[1]; Lopez, Nazario ^[1]; Müller, Peter ^[1]; Wu, Gang ^[2]; Nocera, Daniel G. ^[3]; Cummins, Christopher C. ^[1]

Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139-4307, United States
Department of Chemistry, Queen’s University, 90 Bader Lane, Kingston, Ontario K7L3N6, Canada
Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge Massachusetts 02138, United States

Publication Date:: Thu Nov 12 00:00:00 EST 2015

Research Org.:: Harvard Univ., Cambridge, MA (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Queen's Univ., Kingston, ON (Canada)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Natural Sciences and Engineering Research Council of Canada (NSERC)

OSTI Identifier:: 1225820

Alternate Identifier(s):: OSTI ID: 1437362

Grant/Contract Number:: SC0009565; CHE-1305124; CHE-9808061; DBI-9729592; CHE-0946721

Resource Type:: Published Article

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Name: Journal of the American Chemical Society Journal Volume: 137 Journal Issue: 46; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Nava, Matthew, Lopez, Nazario, Müller, Peter, Wu, Gang, Nocera, Daniel G., and Cummins, Christopher C. Anion-Receptor Mediated Oxidation of Carbon Monoxide to Carbonate by Peroxide Dianion.  United States: N. p., 2015. 
Web.  doi:10.1021/jacs.5b08495.

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                    Nava, Matthew, Lopez, Nazario, Müller, Peter, Wu, Gang, Nocera, Daniel G., & Cummins, Christopher C. Anion-Receptor Mediated Oxidation of Carbon Monoxide to Carbonate by Peroxide Dianion.  United States.  https://doi.org/10.1021/jacs.5b08495

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                    Nava, Matthew, Lopez, Nazario, Müller, Peter, Wu, Gang, Nocera, Daniel G., and Cummins, Christopher C. Thu .  
"Anion-Receptor Mediated Oxidation of Carbon Monoxide to Carbonate by Peroxide Dianion".  United States.  https://doi.org/10.1021/jacs.5b08495.

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@article{osti_1225820,

  title        = {Anion-Receptor Mediated Oxidation of Carbon Monoxide to Carbonate by Peroxide Dianion},

  author       = {Nava, Matthew and Lopez, Nazario and Müller, Peter and Wu, Gang and Nocera, Daniel G. and Cummins, Christopher C.},

  abstractNote = {The reactivity of peroxide dianion O22– has been scarcely explored in organic media due to the lack of soluble sources of this reduced oxygen species. We now report the finding that the encapsulated peroxide cryptate, [O2cmBDCA-5t-H6]2– (1), reacts with carbon monoxide in organic solvents at 40 °C to cleanly form an encapsulated carbonate. Characterization of the resulting hexacarboxamide carbonate cryptate by single crystal X-ray diffraction reveals that carbonate dianion forms nine complementary hydrogen bonds with the hexacarboxamide cryptand, [CO3cmBDCA-5t-H6]2– (2), a conclusion that is supported by spectroscopic data. Labeling studies and 17O solid-state NMR data confirm that two-thirds of the oxygen atoms in the encapsulated carbonate derive from peroxide dianion, while the carbon is derived from CO. Further evidence for the formation of a carbonate cryptate was obtained by three methods of independent synthesis: treatment of (i) free cryptand with K2CO3; (ii) monodeprotonated cryptand with PPN[HCO3]; and (iii) free cryptand with TBA[OH] and atmospheric CO2. This work demonstrates CO oxidation mediated by a hydrogen-bonding anion receptor, constituting an alternative to transition-metal catalysis.},

  doi          = {10.1021/jacs.5b08495},

  journal      = {Journal of the American Chemical Society},

  number       = 46,

  volume       = 137,

  place        = {United States},

  year         = {Thu Nov 12 00:00:00 EST 2015},

  month        = {Thu Nov 12 00:00:00 EST 2015}

}

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