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

The reactivity of peroxide dianion O 2 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, [O 2cmBDCA-5t-H 6] 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, [CO 3cmBDCA-5t-H 6] 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 K 2CO 3; (ii) monodeprotonated cryptand with PPN[HCO 3]; and (iii) free cryptand with TBA[OH] and atmospheric CO 2. This work demonstrates CO oxidation mediated by a hydrogen-bonding anion receptor, constituting an alternative to transition-metal catalysis.
Authors:
 [1] ;  [1] ;  [1] ;  [2] ;  [3] ;  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemistry
  2. Queen's Univ., Kingston, ON (Canada). Dept. of Chemistry
  3. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
Publication Date:
Grant/Contract Number:
SC0009565; CHE-1305124; CHE-9808061; DBI-9729592; CHE-0946721
Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 137; Journal Issue: 46; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
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) (SC-22); National Science Foundation (NSF); Natural Sciences and Engineering Research Council of Canada (NSERC)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1225820
Alternate Identifier(s):
OSTI ID: 1437362

Nava, Matthew, Lopez, Nazario, Muller, 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., Web. doi:10.1021/jacs.5b08495.
Nava, Matthew, Lopez, Nazario, Muller, Peter, Wu, Gang, Nocera, Daniel G., & Cummins, Christopher C.. Anion-Receptor Mediated Oxidation of Carbon Monoxide to Carbonate by Peroxide Dianion. United States. doi:10.1021/jacs.5b08495.
Nava, Matthew, Lopez, Nazario, Muller, Peter, Wu, Gang, Nocera, Daniel G., and Cummins, Christopher C.. 2015. "Anion-Receptor Mediated Oxidation of Carbon Monoxide to Carbonate by Peroxide Dianion". United States. doi:10.1021/jacs.5b08495.
@article{osti_1225820,
title = {Anion-Receptor Mediated Oxidation of Carbon Monoxide to Carbonate by Peroxide Dianion},
author = {Nava, Matthew and Lopez, Nazario and Muller, 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 = {2015},
month = {10}
}