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Title: Selective C-H Functionalization of Methane and Ethane by a Molecular Sb V Complex

Abstract

Owing to the strong nonpolar bonds involved, selective C-H functionalization of methane and ethane to esters remains a challenge for molecular homogeneous chemistry. Here, we report that the computationally predicted main-group p-block SbV (TFA)5 complex selectively functionalizes the C-H bonds of methane and ethane to the corresponding mono and/or diol trifluoroacetate esters at 110-180 °C with yields for ethane of up to 60 % with over 90 % selectivity. Additionally, experimental and computational studies support a unique mechanism that involves SbV -mediated C-H activation followed by functionalization of a SbV -alkyl intermediate.

Authors:
 [1];  [1];  [2];  [1];  [3];  [2]; ORCiD logo [3];  [1]
+ Show Author Affiliations
  1. Scripps Research Inst., Jupiter, FL (United States)
  2. Hyconix Incorp., Chicago, IL (United States)
  3. Brigham Young Univ., Provo, UT (United States)
Publication Date:
Research Org.:
Brigham Young Univ., Provo, UT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1595925
Alternate Identifier(s):
OSTI ID: 1491423
Grant/Contract Number:  
SC0018329
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 8; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; alkanes; antimony; C−H activation; main-group metals; oxidation

Citation Formats

Koppaka, Anjaneyulu, Park, Sae Hume, Hashiguchi, Brian G., Gunsalus, Niles J., King, Clinton R., Konnick, Michael M., Ess, Daniel H., and Periana, Roy A. Selective C-H Functionalization of Methane and Ethane by a Molecular Sb V Complex. United States: N. p., 2018. Web. doi:10.1002/anie.201809159.
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Koppaka, Anjaneyulu, Park, Sae Hume, Hashiguchi, Brian G., Gunsalus, Niles J., King, Clinton R., Konnick, Michael M., Ess, Daniel H., & Periana, Roy A. Selective C-H Functionalization of Methane and Ethane by a Molecular Sb V Complex. United States. https://doi.org/10.1002/anie.201809159
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Koppaka, Anjaneyulu, Park, Sae Hume, Hashiguchi, Brian G., Gunsalus, Niles J., King, Clinton R., Konnick, Michael M., Ess, Daniel H., and Periana, Roy A. Thu . "Selective C-H Functionalization of Methane and Ethane by a Molecular Sb V Complex". United States. https://doi.org/10.1002/anie.201809159. https://www.osti.gov/servlets/purl/1595925.
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@article{osti_1595925,
title = {Selective C-H Functionalization of Methane and Ethane by a Molecular Sb V Complex},
author = {Koppaka, Anjaneyulu and Park, Sae Hume and Hashiguchi, Brian G. and Gunsalus, Niles J. and King, Clinton R. and Konnick, Michael M. and Ess, Daniel H. and Periana, Roy A.},
abstractNote = {Owing to the strong nonpolar bonds involved, selective C-H functionalization of methane and ethane to esters remains a challenge for molecular homogeneous chemistry. Here, we report that the computationally predicted main-group p-block SbV (TFA)5 complex selectively functionalizes the C-H bonds of methane and ethane to the corresponding mono and/or diol trifluoroacetate esters at 110-180 °C with yields for ethane of up to 60 % with over 90 % selectivity. Additionally, experimental and computational studies support a unique mechanism that involves SbV -mediated C-H activation followed by functionalization of a SbV -alkyl intermediate.},
doi = {10.1002/anie.201809159},
journal = {Angewandte Chemie (International Edition)},
number = 8,
volume = 58,
place = {United States},
year = {Thu Dec 27 00:00:00 EST 2018},
month = {Thu Dec 27 00:00:00 EST 2018}
}
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https://doi.org/10.1002/anie.201809159
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