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:
-
- Scripps Research Inst., Jupiter, FL (United States)
- Hyconix Incorp., Chicago, IL (United States)
- 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.
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
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.
@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}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Cited by: 15 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Oxidation of Sb(III) to Sb(V) by O2 and H2O2 in aqueous solutions
journal, March 2005
- Leuz, Ann-Kathrin; Johnson, C. Annette
- Geochimica et Cosmochimica Acta, Vol. 69, Issue 5
The role of databases in support of computational chemistry calculations
journal, October 1996
- Feller, David
- Journal of Computational Chemistry, Vol. 17, Issue 13
Property-optimized Gaussian basis sets for molecular response calculations
journal, October 2010
- Rappoport, Dmitrij; Furche, Filipp
- The Journal of Chemical Physics, Vol. 133, Issue 13
Density Functionals with Broad Applicability in Chemistry
journal, February 2008
- Zhao, Yan; Truhlar, Donald G.
- Accounts of Chemical Research, Vol. 41, Issue 2
Homogeneous Functionalization of Methane
journal, March 2017
- Gunsalus, Niles Jensen; Koppaka, Anjaneyulu; Park, Sae Hume
- Chemical Reviews, Vol. 117, Issue 13
Superacid-catalyzed protium-deuterium exchange in isobutane competing with tert-butyl cation formation
journal, July 1992
- Sommer, Jean; Bukala, Jozef; Rouba, Said
- Journal of the American Chemical Society, Vol. 114, Issue 14
Darstellung, spektroskopische und r�ntgenographische Untersuchung von monomerem Sb(CCCH3)5 und dimerem Sb(OCH3)5
journal, March 1981
- Tempel, N.; Schwarz, W.; Weidlein, J.
- Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 474, Issue 3
Chemistry in super acids. I. Hydrogen exchange and polycondensation of methane and alkanes in FSO3H-SbF5 ("magic acid") solution. Protonation of alkanes and the intermediacy of CH5+ and related hydrocarbon ions. The high chemical reactivity of "paraffins" in ionic solution reactions
journal, May 1968
- Olah, George A.; Schlosberg, Richard H.
- Journal of the American Chemical Society, Vol. 90, Issue 10
DFT Calculations on the Protonation of Alkanes on HF/SbF 5 Superacids Using Cluster Models
journal, May 2001
- Esteves, Pierre M.; Ramírez-Solís, Alejandro; Mota, Claudio J. A.
- The Journal of Physical Chemistry B, Vol. 105, Issue 19
Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions
journal, May 2009
- Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G.
- The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396
Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg
journal, January 1985
- Hay, P. Jeffrey; Wadt, Willard R.
- The Journal of Chemical Physics, Vol. 82, Issue 1
Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals
journal, January 1985
- Hay, P. Jeffrey; Wadt, Willard R.
- The Journal of Chemical Physics, Vol. 82, Issue 1, p. 299-310
The Hammett Acidity Function H 0 for Trifluoroacetic Acid Solutions of Sulfuric and Hydrofluoric Acids 1
journal, April 1959
- Hyman, Herbert H.; Garber, Ronald A.
- Journal of the American Chemical Society, Vol. 81, Issue 8
Selective CH Functionalization of Methane, Ethane, and Propane by a Perfluoroarene Iodine(III) Complex
journal, August 2014
- Konnick, Michael M.; Hashiguchi, Brian G.; Devarajan, Deepa
- Angewandte Chemie, Vol. 126, Issue 39
Reaktionen von Glykolen mit Antimon(V)-acetat und Triphenylstibinoxid. Zwischenprodukte bei der Glykolspaltung
journal, January 1964
- Nerdel, Freidrich; Buddrus, Joachim; Höher, Klaus
- Chemische Berichte, Vol. 97, Issue 1
Detection of pseudorotation in dimers of pentaalkoxy derivatives of antimony on the basis of PMR spectrometric data
journal, March 1983
- Arbuzov, B. A.; Klochkov, V. V.; Aganov, A. V.
- Bulletin of the Academy of Sciences of the USSR Division of Chemical Science, Vol. 32, Issue 3
Addition of Polarization and Diffuse Functions to the LANL2DZ Basis Set for P-Block Elements
journal, August 2001
- Check, Catherine E.; Faust, Timothy O.; Bailey, John M.
- The Journal of Physical Chemistry A, Vol. 105, Issue 34
NMR Spectra of Some Metal Acetylacetonates
journal, July 1967
- Kawasaki, Yoshikane; Tanaka, Toshio; Okawara, Rokuro
- Bulletin of the Chemical Society of Japan, Vol. 40, Issue 7
Basis Set Exchange: A Community Database for Computational Sciences
journal, March 2007
- Schuchardt, Karen L.; Didier, Brett T.; Elsethagen, Todd
- Journal of Chemical Information and Modeling, Vol. 47, Issue 3
Solvated CH5+ in Liquid Superacid
journal, May 2001
- Ahlberg, Per; Karlsson, Annika; Goeppert, Alain
- Chemistry, Vol. 7, Issue 9
Super acids. III. Protonation of alkanes and intermediacy of alkanonium ions, pentacoordinated carbon cations of CH5+ type. Hydrogen exchange, protolytic cleavage, hydrogen abstraction; polycondensation of methane, ethane, 2,2-dimethylpropane and 2,2,3,3-tetramethylbutane in FSO3H-SbF5
journal, June 1969
- Olah, George A.; Klopman, Gilles; Schlosberg, Richard H.
- Journal of the American Chemical Society, Vol. 91, Issue 12
Selective CH Functionalization of Methane, Ethane, and Propane by a Perfluoroarene Iodine(III) Complex
journal, August 2014
- Konnick, Michael M.; Hashiguchi, Brian G.; Devarajan, Deepa
- Angewandte Chemie International Edition, Vol. 53, Issue 39, p. 10490-10494
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007
- Zhao, Yan; Truhlar, Donald G.
- Theoretical Chemistry Accounts, Vol. 120, Issue 1-3
Electrophilic Substitution at methane: Short communication
journal, January 1968
- Hogeveen, H.; Gaasbeek, C. J.
- Recueil des Travaux Chimiques des Pays-Bas, Vol. 87, Issue 3
Superacid-Promoted Ionization of Alkanes Without Carbonium Ion Formation: A Density Functional Theory Study
journal, October 2012
- Dinér, Peter
- The Journal of Physical Chemistry A, Vol. 116, Issue 40
Small-core multiconfiguration-Dirac–Hartree–Fock-adjusted pseudopotentials for post- d main group elements: Application to PbH and PbO
journal, August 2000
- Metz, Bernhard; Stoll, Hermann; Dolg, Michael
- The Journal of Chemical Physics, Vol. 113, Issue 7
H/D isotope exchange between methane and magic acid (HSO 3 F–SbF 5 ): an in situ NMR study
journal, January 2004
- Walspurger, Stéphane; Goeppert, Alain; Haouas, Mohamed
- New J. Chem., Vol. 28, Issue 2
Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi
journal, January 1985
- Wadt, Willard R.; Hay, P. Jeffrey
- The Journal of Chemical Physics, Vol. 82, Issue 1
Hydrocarbon Reactivity in the Superacid SbF 5 /HF: an ab Initio Molecular Dynamics Study
journal, November 2002
- Raugei, Simone; Klein, Michael L.
- The Journal of Physical Chemistry B, Vol. 106, Issue 44
Synthesis and Full Characterization of Molybdenum and Antimony Corroles and Utilization of the Latter Complexes as Very Efficient Catalysts for Highly Selective Aerobic Oxygenation Reactions
journal, January 2006
- Luobeznova, Inna; Raizman, Marina; Goldberg, Israel
- Inorganic Chemistry, Vol. 45, Issue 1
Hexakis(pentafluorooxotellurato)pnictate(V) Anions, M(OTeF5)6- (M = As, Sb, Bi): A Series of Very Weakly Coordinating Anions
journal, April 1994
- Mercier, Helene P. A.; Sanders, Jeremy C. P.; Schrobilgen, Gary J.
- Journal of the American Chemical Society, Vol. 116, Issue 7
Methane Manifesto: A Theorist’s Perspective on Catalytic Light Alkane Functionalization
journal, September 2016
- Cundari, Thomas R.
- Comments on Inorganic Chemistry, Vol. 37, Issue 5
Main-Group Compounds Selectively Oxidize Mixtures of Methane, Ethane, and Propane to Alcohol Esters
journal, March 2014
- Hashiguchi, B. G.; Konnick, M. M.; Bischof, S. M.
- Science, Vol. 343, Issue 6176, p. 1232-1237
Solvated CH5+ in Liquid Superacid
journal, June 2001
- Ahlberg, Per; Karlsson, Annika; Goeppert, Alain
- Chemistry - A European Journal, Vol. 7, Issue 12
Works referencing / citing this record:
Selective Photo‐Oxygenation of Light Alkanes Using Iodine Oxides and Chloride
journal, September 2019
- Liebov, Nichole S.; Goldberg, Jonathan M.; Boaz, Nicholas C.
- ChemCatChem, Vol. 11, Issue 20
From a 1D Sb Coordination Polymer to a 3D Sb Framework with Pyrazine: Switching off the Stereochemically Active Lone-Pair: From a 1D Sb Coordination Polymer to a 3D Sb Framework with Pyrazine: Switching off the Stereochemically Active Lone-Pair
journal, May 2020
- Sorg, Jens R.; Schäfer, Thomas C.; Schneider, Tilman
- Zeitschrift für anorganische und allgemeine Chemie, Vol. 646, Issue 11-12
Establishing the correlation between catalytic performance and N→Sb donor–acceptor interaction: systematic assessment of azastibocine halide derivatives as water tolerant Lewis acids
journal, January 2019
- Lei, Jian; Peng, Lingteng; Qiu, Renhua
- Dalton Transactions, Vol. 48, Issue 23
Unveiling the potential of scandium complexes for methane C–H bond activation: a computational study
journal, January 2019
- de Lima Batista, Ana Paula; S. de Oliveira-Filho, Antonio G.; Braga, Ataualpa A. C.
- New Journal of Chemistry, Vol. 43, Issue 31