Selective C−H Functionalization of Methane and Ethane by a Molecular Sb V Complex

Koppaka, Anjaneyulu; Park, Sae Hume; Hashiguchi, Brian G.; Gunsalus, Niles J.; King, Clinton R.; Konnick, Michael M.; Ess, Daniel H.; Periana, Roy A.

doi:10.1002/ange.201809159

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

Journal Article · Mon Jan 21 00:00:00 EST 2019 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201809159· OSTI ID:1491424

Koppaka, Anjaneyulu ^[1]; Park, Sae Hume ^[1]; Hashiguchi, Brian G. ^[2]; Gunsalus, Niles J. ^[1]; King, Clinton R. ^[3]; Konnick, Michael M. ^[2];

^[3]; Periana, Roy A. ^[1]

The Scripps Energy and Materials Center Department of Chemistry The Scripps Research Institute Jupiter FL 33458 USA
Hyconix Incorporation 205 North Michigan Avenue, Suite 2930 Chicago IL 60601 USA
Department of Chemistry and Biochemistry Brigham Young University (BYU) Provo UT 84602 USA

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. We report that the computationally predicted main‐group p ‐block Sb ^V (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. Experimental and computational studies support a unique mechanism that involves Sb ^V ‐mediated C−H activation followed by functionalization of a Sb ^V ‐alkyl intermediate.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0018329

OSTI ID:: 1491424

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 131 Journal Issue: 8; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (34)

Oxidation of Sb(III) to Sb(V) by O2 and H2O2 in aqueous solutions Leuz, Ann-Kathrin; Johnson, C. Annette Geochimica et Cosmochimica Acta, Vol. 69, Issue 5 https://doi.org/10.1016/j.gca.2004.08.019	journal	March 2005
C–H activation Bergman, Robert G. Nature, Vol. 446, Issue 7134 https://doi.org/10.1038/446391a	journal	March 2007
The role of databases in support of computational chemistry calculations Feller, David Journal of Computational Chemistry, Vol. 17, Issue 13 https://doi.org/10.1002/(SICI)1096-987X(199610)17:13<1571::AID-JCC9>3.0.CO;2-P	journal	October 1996
Property-optimized Gaussian basis sets for molecular response calculations Rappoport, Dmitrij; Furche, Filipp The Journal of Chemical Physics, Vol. 133, Issue 13 https://doi.org/10.1063/1.3484283	journal	October 2010
Density Functionals with Broad Applicability in Chemistry Zhao, Yan; Truhlar, Donald G. Accounts of Chemical Research, Vol. 41, Issue 2 https://doi.org/10.1021/ar700111a	journal	February 2008
Homogeneous Functionalization of Methane Gunsalus, Niles Jensen; Koppaka, Anjaneyulu; Park, Sae Hume Chemical Reviews, Vol. 117, Issue 13 https://doi.org/10.1021/acs.chemrev.6b00739	journal	March 2017
Superacid-catalyzed protium-deuterium exchange in isobutane competing with tert-butyl cation formation Sommer, Jean; Bukala, Jozef; Rouba, Said Journal of the American Chemical Society, Vol. 114, Issue 14 https://doi.org/10.1021/ja00040a075	journal	July 1992
Darstellung, spektroskopische und r�ntgenographische Untersuchung von monomerem Sb(CCCH3)5 und dimerem Sb(OCH3)5 Tempel, N.; Schwarz, W.; Weidlein, J. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 474, Issue 3 https://doi.org/10.1002/zaac.19814740316	journal	March 1981
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 Olah, George A.; Schlosberg, Richard H. Journal of the American Chemical Society, Vol. 90, Issue 10 https://doi.org/10.1021/ja01012a066	journal	May 1968
DFT Calculations on the Protonation of Alkanes on HF/SbF ₅ Superacids Using Cluster Models Esteves, Pierre M.; Ramírez-Solís, Alejandro; Mota, Claudio J. A. The Journal of Physical Chemistry B, Vol. 105, Issue 19 https://doi.org/10.1021/jp004310f	journal	May 2001
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 Marenich, Aleksandr V.; Cramer, Christopher J.; Truhlar, Donald G. The Journal of Physical Chemistry B, Vol. 113, Issue 18, p. 6378-6396 https://doi.org/10.1021/jp810292n	journal	May 2009
Ab initio effective core potentials for molecular calculations. Potentials for the transition metal atoms Sc to Hg Hay, P. Jeffrey; Wadt, Willard R. The Journal of Chemical Physics, Vol. 82, Issue 1 https://doi.org/10.1063/1.448799	journal	January 1985
Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals Hay, P. Jeffrey; Wadt, Willard R. The Journal of Chemical Physics, Vol. 82, Issue 1, p. 299-310 https://doi.org/10.1063/1.448975	journal	January 1985
The Hammett Acidity Function H ₀ for Trifluoroacetic Acid Solutions of Sulfuric and Hydrofluoric Acids ¹ Hyman, Herbert H.; Garber, Ronald A. Journal of the American Chemical Society, Vol. 81, Issue 8 https://doi.org/10.1021/ja01517a019	journal	April 1959
Selective CH Functionalization of Methane, Ethane, and Propane by a Perfluoroarene Iodine(III) Complex Konnick, Michael M.; Hashiguchi, Brian G.; Devarajan, Deepa Angewandte Chemie, Vol. 126, Issue 39 https://doi.org/10.1002/ange.201406185	journal	August 2014
Reaktionen von Glykolen mit Antimon(V)-acetat und Triphenylstibinoxid. Zwischenprodukte bei der Glykolspaltung Nerdel, Freidrich; Buddrus, Joachim; Höher, Klaus Chemische Berichte, Vol. 97, Issue 1 https://doi.org/10.1002/cber.19640970117	journal	January 1964
Detection of pseudorotation in dimers of pentaalkoxy derivatives of antimony on the basis of PMR spectrometric data 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 https://doi.org/10.1007/BF00953079	journal	March 1983
Addition of Polarization and Diffuse Functions to the LANL2DZ Basis Set for P-Block Elements Check, Catherine E.; Faust, Timothy O.; Bailey, John M. The Journal of Physical Chemistry A, Vol. 105, Issue 34 https://doi.org/10.1021/jp011945l	journal	August 2001
NMR Spectra of Some Metal Acetylacetonates Kawasaki, Yoshikane; Tanaka, Toshio; Okawara, Rokuro Bulletin of the Chemical Society of Japan, Vol. 40, Issue 7 https://doi.org/10.1246/bcsj.40.1562	journal	July 1967
Basis Set Exchange: A Community Database for Computational Sciences Schuchardt, Karen L.; Didier, Brett T.; Elsethagen, Todd Journal of Chemical Information and Modeling, Vol. 47, Issue 3 https://doi.org/10.1021/ci600510j	journal	March 2007
Solvated CH5+ in Liquid Superacid Ahlberg, Per; Karlsson, Annika; Goeppert, Alain Chemistry, Vol. 7, Issue 9 https://doi.org/10.1002/1521-3765(20010504)7:9<1936::AID-CHEM1936>3.0.CO;2-T	journal	May 2001
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 Olah, George A.; Klopman, Gilles; Schlosberg, Richard H. Journal of the American Chemical Society, Vol. 91, Issue 12 https://doi.org/10.1021/ja01040a029	journal	June 1969
Selective CH Functionalization of Methane, Ethane, and Propane by a Perfluoroarene Iodine(III) Complex Konnick, Michael M.; Hashiguchi, Brian G.; Devarajan, Deepa Angewandte Chemie International Edition, Vol. 53, Issue 39, p. 10490-10494 https://doi.org/10.1002/anie.201406185	journal	August 2014
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 Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Electrophilic Substitution at methane: Short communication Hogeveen, H.; Gaasbeek, C. J. Recueil des Travaux Chimiques des Pays-Bas, Vol. 87, Issue 3 https://doi.org/10.1002/recl.19680870311	journal	January 1968
Superacid-Promoted Ionization of Alkanes Without Carbonium Ion Formation: A Density Functional Theory Study Dinér, Peter The Journal of Physical Chemistry A, Vol. 116, Issue 40 https://doi.org/10.1021/jp306319s	journal	October 2012
Small-core multiconfiguration-Dirac–Hartree–Fock-adjusted pseudopotentials for post- d main group elements: Application to PbH and PbO Metz, Bernhard; Stoll, Hermann; Dolg, Michael The Journal of Chemical Physics, Vol. 113, Issue 7 https://doi.org/10.1063/1.1305880	journal	August 2000
H/D isotope exchange between methane and magic acid (HSO ₃ F–SbF ₅ ): an in situ NMR study Walspurger, Stéphane; Goeppert, Alain; Haouas, Mohamed New J. Chem., Vol. 28, Issue 2 https://doi.org/10.1039/B309362J	journal	January 2004
Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi Wadt, Willard R.; Hay, P. Jeffrey The Journal of Chemical Physics, Vol. 82, Issue 1 https://doi.org/10.1063/1.448800	journal	January 1985
Hydrocarbon Reactivity in the Superacid SbF ₅ /HF: an ab Initio Molecular Dynamics Study Raugei, Simone; Klein, Michael L. The Journal of Physical Chemistry B, Vol. 106, Issue 44 https://doi.org/10.1021/jp026395l	journal	November 2002
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 Luobeznova, Inna; Raizman, Marina; Goldberg, Israel Inorganic Chemistry, Vol. 45, Issue 1 https://doi.org/10.1021/ic051483g	journal	January 2006
Hexakis(pentafluorooxotellurato)pnictate(V) Anions, M(OTeF5)6- (M = As, Sb, Bi): A Series of Very Weakly Coordinating Anions Mercier, Helene P. A.; Sanders, Jeremy C. P.; Schrobilgen, Gary J. Journal of the American Chemical Society, Vol. 116, Issue 7 https://doi.org/10.1021/ja00086a025	journal	April 1994
Methane Manifesto: A Theorist’s Perspective on Catalytic Light Alkane Functionalization Cundari, Thomas R. Comments on Inorganic Chemistry, Vol. 37, Issue 5 https://doi.org/10.1080/02603594.2016.1242487	journal	September 2016
Main-Group Compounds Selectively Oxidize Mixtures of Methane, Ethane, and Propane to Alcohol Esters Hashiguchi, B. G.; Konnick, M. M.; Bischof, S. M. Science, Vol. 343, Issue 6176, p. 1232-1237 https://doi.org/10.1126/science.1249357	journal	March 2014

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