Direct functionalization of C-H bonds by electrophilic anions

Warneke, Jonas; Mayer, Martin; Rohdenburg, Markus; Ma, Xin; Liu, Judy K.; Grellmann, Max; Debnath, Sreekanta; Azov, Vladimir A.; Apra, Edoardo; Young, Robert P.; Jenne, Carsten; Johnson, Grant E.; Kenttamaa, Hilkka I.; Asmis, Knut R.; Laskin, Julia

doi:10.1073/pnas.2004432117

Title: Direct functionalization of C-H bonds by electrophilic anions

Journal Article · Tue Sep 22 00:00:00 EDT 2020 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.2004432117· OSTI ID:1681224

Warneke, Jonas ^[1]; Mayer, Martin ^[2]; Rohdenburg, Markus ^[3]; Ma, Xin ^[4]; Liu, Judy K. ^[4]; Grellmann, Max ^[2]; Debnath, Sreekanta ^[5]; Azov, Vladimir A. ^[6];

^[7];

^[7]; Jenne, Carsten ^[8];

^[7]; Kenttamaa, Hilkka I. ^[4]; Asmis, Knut R. ^[2]; Laskin, Julia ^[4]

UNIVERSITY PROGRAMS
Universitat Leipzig
Universitat Bremen
Purdue University
Fritz-Haber-Institut der Max-Plank-Gesellschaft
Universiteit van die Vrystaat
BATTELLE (PACIFIC NW LAB)
Bergische Universitat Wuppertal

Bond formation between two of the most inert molecules, alkanes and [B12X12]2- (X = Cl, Br), is performed in a two step process. Fragmentation of [B12X12]2- in the gas phase generates highly reactive [B12X11]- ions which spontaneously react with alkanes. The reaction mechanism was investigated using tandem mass spectrometry and gas-phase vibrational spectroscopy combined with electronic structure calculations. This effort revealed the unprecedented and counterintuitive electrophilic substitution of a proton in an alkane by a negatively charged ion resulting in a B-C bond formation. The product is a dianionic [B12X11CnH2n+1]2- species, in which H+ is electrostatically bound to the dianion. High flux ion soft-landing was performed to co-deposit [B12X11]- and complex organic molecules (phthalates) in thin layers on surfaces. Molecular structure analysis of the product films revealed that C-H functionalization by [B12X11]- occured in the presence of other more reactive functional groups. This observation demonstrates the utility of highly reactive fragment ions for defined bond formation processes and may pave the way to the use of gas phase ion chemistry for chemical synthesis in the condensed phase.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1681224

Report Number(s):: PNNL-SA-149918

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 117, Issue 38

Country of Publication:: United States

Language:: English

References (44)

Designing Catalysts for Functionalization of Unactivated C–H Bonds Based on the CH Activation Reaction Hashiguchi, Brian G.; Bischof, Steven M.; Konnick, Michael M. Accounts of Chemical Research, Vol. 45, Issue 6 https://doi.org/10.1021/ar200250r	journal	January 2012
Electronic Effects on Room-Temperature, Gas-Phase C–H Bond Activations by Cluster Oxides and Metal Carbides: The Methane Challenge Schwarz, Helmut; Shaik, Sason; Li, Jilai Journal of the American Chemical Society, Vol. 139, Issue 48 https://doi.org/10.1021/jacs.7b10139	journal	November 2017
Activation of C−H Bonds by Metal Complexes Shilov, Alexander E.; Shul'pin, Georgiy B. Chemical Reviews, Vol. 97, Issue 8 https://doi.org/10.1021/cr9411886	journal	December 1997
How and Why Do Cluster Size, Charge State, and Ligands Affect the Course of Metal-Mediated Gas-Phase Activation of Methane? Schwarz, Helmut Israel Journal of Chemistry, Vol. 54, Issue 10 https://doi.org/10.1002/ijch.201300134	journal	July 2014
Complete cleavage of the N≡N triple bond by Ta ₂ N ⁺ via degenerate ligand exchange at ambient temperature: A perfect catalytic cycle Geng, Caiyun; Li, Jilai; Weiske, Thomas Proceedings of the National Academy of Sciences, Vol. 116, Issue 43 https://doi.org/10.1073/pnas.1913664116	journal	October 2019
The Process of Tholin Formation in Titan's Upper Atmosphere Waite, J. H.; Young, D. T.; Cravens, T. E. Science, Vol. 316, Issue 5826 https://doi.org/10.1126/science.1139727	journal	May 2007
Nucleophilic Addition of Nitrogen to Aryl Cations: Mimicking Titan Chemistry Li, Anyin; Jjunju, Fred P. M.; Cooks, R. Graham Journal of The American Society for Mass Spectrometry, Vol. 24, Issue 11 https://doi.org/10.1007/s13361-013-0710-1	journal	August 2013
Superacidity of Boron Acids H ₂ (B ₁₂ X ₁₂ ) (X=Cl, Br) Avelar, Amy; Tham, Fook S.; Reed, Christopher A. Angewandte Chemie International Edition, Vol. 48, Issue 19 https://doi.org/10.1002/anie.200900214	journal	April 2009
Synthesis, Crystal Structure, and Reactivity of the Strong Methylating Agent Me2B12Cl12 Bolli, Christoph; Derendorf, Janis; Keßler, Mathias Angewandte Chemie International Edition, Vol. 49, Issue 20 https://doi.org/10.1002/anie.200906627	journal	April 2010
Applications of Radiolabeled Boron Clusters to the Diagnosis and Treatment of Cancer Hawthorne, M. Frederick; Maderna, Andreas Chemical Reviews, Vol. 99, Issue 12 https://doi.org/10.1021/cr980442h	journal	December 1999
Boron Chemistry Lights the Way: Optical Properties of Molecular and Polymeric Systems C.D.E. thanks EPSRC for a postgraduate studentship and Syngenta for a postgraduate scholarship, and T.B.M. thanks the University of Durham for support and Prof. Dr. K. Tamao for a preprint of ref. 32. Entwistle, Christopher D.; Marder, Todd B. Angewandte Chemie International Edition, Vol. 41, Issue 16 https://doi.org/10.1002/1521-3773(20020816)41:16<2927::AID-ANIE2927>3.0.CO;2-L	journal	August 2002
Collision-induced gas-phase reactions of perhalogenated closo-dodecaborate clusters – a comparative study Warneke, Jonas; Dülcks, Thomas; Knapp, Carsten Physical Chemistry Chemical Physics, Vol. 13, Issue 13 https://doi.org/10.1039/c0cp02386h	journal	January 2011
Rational design of an argon-binding superelectrophilic anion Mayer, Martin; van Lessen, Valentin; Rohdenburg, Markus Proceedings of the National Academy of Sciences, Vol. 116, Issue 17 https://doi.org/10.1073/pnas.1820812116	journal	April 2019
Gas-phase activation of methane by ligated transition-metal cations Schroder, D.; Schwarz, H. Proceedings of the National Academy of Sciences, Vol. 105, Issue 47 https://doi.org/10.1073/pnas.0801849105	journal	October 2008
Electrophilic, Ambiphilic, and Nucleophilic C−H Bond Activation: Understanding the Electronic Continuum of C−H Bond Activation Through Transition-State and Reaction Pathway Interaction Energy Decompositions Ess, Daniel H.; Goddard, William A.; Periana, Roy A. Organometallics, Vol. 29, Issue 23 https://doi.org/10.1021/om100879y	journal	December 2010
Protic Anions [H(B ₁₂ X ₁₂ )] ⁻ (X=F, Cl, Br, I) That Act as Brønsted Acids in the Gas Phase Jenne, Carsten; Keßler, Mathias; Warneke, Jonas Chemistry - A European Journal, Vol. 21, Issue 15 https://doi.org/10.1002/chem.201500034	journal	March 2015
Superacidity of closo -Dodecaborate-Based Brønsted Acids: a DFT Study Lipping, Lauri; Leito, Ivo; Koppel, Ivar The Journal of Physical Chemistry A, Vol. 119, Issue 4 https://doi.org/10.1021/jp506485x	journal	January 2015
Gas-Phase Infrared Spectrum of the Protonated Water Dimer Asmis, K. R. Science, Vol. 299, Issue 5611 https://doi.org/10.1126/science.1081634	journal	February 2003
The Essential Role of Bond Energetics in C–H Activation/Functionalization Xue, Xiao-Song; Ji, Pengju; Zhou, Biying Chemical Reviews, Vol. 117, Issue 13 https://doi.org/10.1021/acs.chemrev.6b00664	journal	March 2017
Selective electrophilic activation of alkanes Sommer, Jean; Bukala, Jozef Accounts of Chemical Research, Vol. 26, Issue 7 https://doi.org/10.1021/ar00031a003	journal	July 1993
Polyhalomethanes Combined with Lewis Acids in Alkane Chemistry Akhrem, Irena; Orlinkov, Alexander Chemical Reviews, Vol. 107, Issue 5 https://doi.org/10.1021/cr970005n	journal	May 2007
Methane Activation by Gas Phase Atomic Clusters Zhao, Yan-Xia; Li, Zi-Yu; Yang, Yuan Accounts of Chemical Research, Vol. 51, Issue 11 https://doi.org/10.1021/acs.accounts.8b00403	journal	October 2018
Mechanistic Analysis of Iridium Heteroatom C−H Activation: Evidence for an Internal Electrophilic Substitution Mechanism Oxgaard, Jonas; Tenn, William J.; Nielsen, Robert J. Organometallics, Vol. 26, Issue 7 https://doi.org/10.1021/om061189b	journal	March 2007
Methane activation by gold-doped titanium oxide cluster anions with closed-shell electronic structures Zhao, Yan-Xia; Li, Xiao-Na; Yuan, Zhen Chemical Science, Vol. 7, Issue 7 https://doi.org/10.1039/C6SC00539J	journal	January 2016
Thermal activation of methane by vanadium boride cluster cations VB _n ⁺ ( n = 3–6) Chen, Qiang; Zhao, Yan-Xia; Jiang, Li-Xue Physical Chemistry Chemical Physics, Vol. 20, Issue 7 https://doi.org/10.1039/C8CP00071A	journal	January 2018
Boron: Its Role in Energy‐Related Processes and Applications Huang, Zhenguo; Wang, Suning; Dewhurst, Rian D. Angewandte Chemie International Edition, Vol. 59, Issue 23 https://doi.org/10.1002/anie.201911108	journal	April 2020
From Isolated Ions to Multilayer Functional Materials Using Ion Soft Landing Laskin, Julia; Johnson, Grant E.; Warneke, Jonas Angewandte Chemie International Edition, Vol. 57, Issue 50 https://doi.org/10.1002/anie.201712296	journal	November 2018
Design and performance of a high-flux electrospray ionization source for ion soft landing Gunaratne, K. Don D.; Prabhakaran, Venkateshkumar; Ibrahim, Yehia M. The Analyst, Vol. 140, Issue 9 https://doi.org/10.1039/C5AN00220F	journal	January 2015
Atomically precise (catalytic) particles synthesized by a novel cluster deposition instrument Yin, C.; Tyo, E.; Kuchta, K. The Journal of Chemical Physics, Vol. 140, Issue 17, Article No. 174201 https://doi.org/10.1063/1.4871799	journal	May 2014
Note: Proof of principle of a new type of cluster beam source with potential for scale-up Palmer, R. E.; Cao, L.; Yin, F. Review of Scientific Instruments, Vol. 87, Issue 4 https://doi.org/10.1063/1.4947229	journal	April 2016
A hydrodynamically optimized nano-electrospray ionization source and vacuum interface Pauly, M.; Sroka, M.; Reiss, J. The Analyst, Vol. 139, Issue 8 https://doi.org/10.1039/c3an01836a	journal	January 2014
Bombardment induced ion transport—Part II. Experimental potassium ion conductivities in borosilicate glass Menezes, P. V.; Martin, J.; Schäfer, M. Physical Chemistry Chemical Physics, Vol. 13, Issue 45 https://doi.org/10.1039/c1cp21216h	journal	January 2011
Solid C58 films Böttcher, Artur; Weis, Patrick; Jester, Stefan-S. Physical Chemistry Chemical Physics, Vol. 7, Issue 14 https://doi.org/10.1039/b505703e	journal	January 2005
Self-organizing layers from complex molecular anions Warneke, Jonas; McBriarty, Martin E.; Riechers, Shawn L. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04228-2	journal	May 2018
Cryogenic ion trap vibrational spectroscopy of hydrogen-bonded clusters relevant to atmospheric chemistry Heine, Nadja; Asmis, Knut R. International Reviews in Physical Chemistry, Vol. 34, Issue 1 https://doi.org/10.1080/0144235X.2014.979659	journal	December 2014
Cryogenic Ion Trap Vibrational Spectroscopy of Hydrogen-Bonded Clusters Relevant to Atmospheric Chemistry ( International Reviews in Physical Chemistry , 2015, Vol. 34, No. 1, 1–34) Heine, Nadja; Asmis, Knut R. International Reviews in Physical Chemistry, Vol. 35, Issue 3 https://doi.org/10.1080/0144235X.2016.1203533	journal	July 2016
Collisionless Multiphoton Dissociation of S $F_{6}$ : A Statistical Thermodynamic Process Black, Jerry G.; Yablonovitch, Eli; Bloembergen, N. Physical Review Letters, Vol. 38, Issue 20 https://doi.org/10.1103/PhysRevLett.38.1131	journal	May 1977
Is Multiphoton Dissociation of Molecules a Statistical Thermal Process? Grant, E. R.; Schulz, P. A.; Sudbo, Aa. S. Physical Review Letters, Vol. 40, Issue 2 https://doi.org/10.1103/PhysRevLett.40.115	journal	January 1978
Multiple-Photon Infrared Laser Photophysics and Photochemistry. I Bagratashvili, V. N.; Letokhov, V. S.; Makarov, A. A. Laser Chemistry, Vol. 1, Issue 5 https://doi.org/10.1155/LC.1.211	journal	January 1983
10 K Ring Electrode Trap—Tandem Mass Spectrometer for Infrared Spectroscopy of Mass Selected Ions Goebbert, Daniel J.; Meijer, Gerard; Asmis, Knut R. 4TH INTERNATIONAL CONFERENCE ON LASER PROBING—LAP 2008, AIP Conference Proceedings https://doi.org/10.1063/1.3115605	conference	January 2009
Messenger-Tagging Electrosprayed Ions: Vibrational Spectroscopy of Suberate Dianions Goebbert, Daniel J.; Wende, Torsten; Bergmann, Risshu The Journal of Physical Chemistry A, Vol. 113, Issue 20 https://doi.org/10.1021/jp809390x	journal	May 2009
The new IR and THz FEL facility at the Fritz Haber Institute in Berlin Schöllkopf, Wieland; Gewinner, Sandy; Junkes, Heinz SPIE Optics + Optoelectronics, SPIE Proceedings https://doi.org/10.1117/12.2182284	conference	May 2015
Synthesis and characterization of synthetically useful salts of the weakly-coordinating dianion [B12Cl12]2− Geis, Vanessa; Guttsche, Kristin; Knapp, Carsten Dalton Transactions, Issue 15 https://doi.org/10.1039/b821030f	journal	January 2009
Die Kristallstrukturen der Dicaesium-Dodekahalogeno-closo-Dodekaborate Cs2[B12X12] (X = Cl, Br, I) und ihrer Hydrate Tiritiris, Ioannis; Schleid, Thomas Zeitschrift für anorganische und allgemeine Chemie, Vol. 630, Issue 11 https://doi.org/10.1002/zaac.200400167	journal	September 2004

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