Abstraction of Hydride from Alkanes and Dihydrogen by the Perfluorotrityl Cation

Leong, Derek W.; Gogoi, Achyut R.; Maity, Tapas; Lee, Chun‐I; Bhuvanesh, Nattamai; Gutierrez, Osvaldo; Ozerov, Oleg V.

doi:10.1002/ange.202422190

Title: Abstraction of Hydride from Alkanes and Dihydrogen by the Perfluorotrityl Cation

Journal Article · 01 March 2025 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202422190 · OSTI ID:2530673

Leong, Derek W. ^[1]; Gogoi, Achyut R. ^[1]; Maity, Tapas ^[1]; Lee, Chun‐I ^[1]; Bhuvanesh, Nattamai ^[1]; Gutierrez, Osvaldo ^[1];

^[1]

Department of Chemistry Texas A&,M University TAMU – 3255 College Station Texas USA 77842

Abstract Lewis acids play a central role in a large variety of chemical transformations. The reactivity of the strongest Lewis acids is typically studied in the context of affinity towards hard bases, such as fluoride or oxygenous species. Carbocations can be viewed as soft Lewis acids, possessing significant affinity for softer bases, such as hydride. This work presents the ambient‐temperature isolation of salts of the perfluorotrityl cation ((C ₆ F ₅ ) ₃ C ⁺ or F ₁₅ Tr ⁺ ) in combination with halogenated carborane anions. The F ₁₅ Tr ⁺ cation exhibits remarkable hydride affinity, illustrated by the observation of hydride abstraction from dihydrogen, and of the rapid abstraction of hydride from −CH ₂ −groups in alkanes. Theoretical studies support the favorability of hydride abstraction from dihydrogen, and indicate that the hydride abstraction from alkanes proceeds via a concerted hydride transfer process that is sensitive to steric effects.

View Journal Article

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0023280

OSTI ID:: 2530673

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 15 Vol. 137; ISSN 0044-8249

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

Country of Publication:: Germany

Language:: English

References (40)

Carbocation Chemistry Olah, George A.; Surya Prakash, G. K. https://doi.org/10.1002/9780471678656	book	October 2004
Strategic Applications of the β‐Silicon Effect Roberts, Dean D.; McLaughlin, Mark G. Advanced Synthesis & Catalysis, Vol. 364, Issue 14 https://doi.org/10.1002/adsc.202200237	journal	June 2022
The Strongest Isolable Acid Juhasz, Mark; Hoffmann, Stephan; Stoyanov, Evgenii Angewandte Chemie International Edition, Vol. 43, Issue 40 https://doi.org/10.1002/anie.200460005	journal	October 2004
Frustrated Lewis Pair Chemistry: Development and Perspectives Stephan, Douglas W.; Erker, Gerhard Angewandte Chemie International Edition, Vol. 54, Issue 22 https://doi.org/10.1002/anie.201409800	journal	May 2015
Taming the Cationic Beast: Novel Developments in the Synthesis and Application of Weakly Coordinating Anions Riddlestone, Ian M.; Kraft, Anne; Schaefer, Julia Angewandte Chemie International Edition, Vol. 57, Issue 43 https://doi.org/10.1002/anie.201710782	journal	September 2018
Frustrated Radical Pairs: Insights from EPR Spectroscopy Dasgupta, Ayan; Richards, Emma; Melen, Rebecca L. Angewandte Chemie International Edition, Vol. 60, Issue 1 https://doi.org/10.1002/anie.202010633	journal	November 2020
The Tris(pentafluorophenyl)methylium Cation: Isolation and Reactivity Hoffmann, Kurt F.; Battke, David; Golz, Paul Angewandte Chemie International Edition, Vol. 61, Issue 28 https://doi.org/10.1002/anie.202203777	journal	May 2022
Halogenated Trityl Cations as Easy‐to‐Access Super Electrophiles Schlögl, Johanna; Brosius, Amelie L.; Toraman, Ahmet N. Angewandte Chemie International Edition https://doi.org/10.1002/anie.202423857	journal	January 2025
Revisiting the Perfluorinated Trityl Cation Delany, Eoghan G.; Kaur, Satnam; Cummings, Steven Chemistry – A European Journal, Vol. 25, Issue 20 https://doi.org/10.1002/chem.201806110	journal	March 2019
Is the Perfluorinated Trityl Cation Worth a Revisit? A Theoretical Study on the Lewis Acidities and Stabilities of Highly Halogenated Trityl Derivatives Couchman, Shannon A.; Wilson, David J. D.; Dutton, Jason L. European Journal of Organic Chemistry, Vol. 2014, Issue 18 https://doi.org/10.1002/ejoc.201402263	journal	May 2014
A comprehensive view on stabilities and reactivities of triarylmethyl cations (tritylium ions) Horn, Markus; Mayr, Herbert Journal of Physical Organic Chemistry, Vol. 25, Issue 11 https://doi.org/10.1002/poc.2979	journal	June 2012
Cationic Two-Coordinate Complexes of Pd(I) and Pt(I) Have Longer Metal-Ligand Bonds Than Their Neutral Counterparts MacInnis, Morgan C.; DeMott, Jessica C.; Zolnhofer, Eva M. Chem, Vol. 1, Issue 6 https://doi.org/10.1016/j.chempr.2016.11.007	journal	December 2016
Silylium Ions: From Elusive Reactive Intermediates to Potent Catalysts Klare, Hendrik F. T.; Albers, Lena; Süsse, Lars Chemical Reviews, Vol. 121, Issue 10 https://doi.org/10.1021/acs.chemrev.0c00855	journal	April 2021
Thermodynamic Hydricity of Transition Metal Hydrides Wiedner, Eric S.; Chambers, Matthew B.; Pitman, Catherine L. Chemical Reviews, Vol. 116, Issue 15 https://doi.org/10.1021/acs.chemrev.6b00168	journal	June 2016
Nonclassical Applications of closo -Carborane Anions: From Main Group Chemistry and Catalysis to Energy Storage Fisher, S. P.; Tomich, A. W.; Lovera, S. O. Chemical Reviews, Vol. 119, Issue 14 https://doi.org/10.1021/acs.chemrev.8b00551	journal	February 2019
Tris(pentafluorophenyl)borane and Beyond: Modern Advances in Borylation Chemistry Lawson, James R.; Melen, Rebecca L. Inorganic Chemistry, Vol. 56, Issue 15 https://doi.org/10.1021/acs.inorgchem.6b02911	journal	February 2017
Optimizing the Energetics of FLP-Type H₂ Activation by Modulating the Electronic and Structural Properties of the Lewis Acids: A DFT Study Heshmat, Mojgan; Ensing, Bernd The Journal of Physical Chemistry A, Vol. 124, Issue 32 https://doi.org/10.1021/acs.jpca.0c03108	journal	July 2020
Cocatalysts for Metal-Catalyzed Olefin Polymerization: Activators, Activation Processes, and Structure−Activity Relationships Chen, Eugene You-Xian; Marks, Tobin J. Chemical Reviews, Vol. 100, Issue 4, p. 1391-1434 https://doi.org/10.1021/cr980462j	journal	April 2000
Perfluoroaromatics. Tris(polyfluoroaryl) carbocations Kulkarni, Shrikant V.; Schure, Ralph.; Filler, Robert. Journal of the American Chemical Society, Vol. 95, Issue 6 https://doi.org/10.1021/ja00787a027	journal	March 1973
Tris(pentafluorophenyl)methyl Cation Filler, Robert.; Wang, Chen-Shen.; McKinney, Michael A. Journal of the American Chemical Society, Vol. 89, Issue 4 https://doi.org/10.1021/ja00980a048	journal	February 1967
Stable Carbonium Ions. XXXV.¹ Pentafluorophenylcarbonium Ions Olah, George A.; Comisarow, Melvin B. Journal of the American Chemical Society, Vol. 89, Issue 4 https://doi.org/10.1021/ja00980a049	journal	February 1967
Stable carbonium ions. XXXIV. 1-Methylcyclopentyl cation Olah, George A.; Bollinger, J. Martin.; Cupas, Chris A. Journal of the American Chemical Society, Vol. 89, Issue 11 https://doi.org/10.1021/ja00987a034	journal	May 1967
Carbonium ion-silane hydride transfer reactions. I. Scope and stereochemistry Carey, Francis A.; Tremper, Henry S. Journal of the American Chemical Society, Vol. 90, Issue 10 https://doi.org/10.1021/ja01012a023	journal	May 1968
Et₂Al⁺ Alumenium Ion-like Chemistry. Synthesis and Reactivity toward Alkenes and Alkene Oxides Kim, Kee-Chan; Reed, Christopher A.; Long, Gregory S. Journal of the American Chemical Society, Vol. 124, Issue 26 https://doi.org/10.1021/ja0259990	journal	June 2002
The Structure of the Strongest Brønsted Acid: The Carborane Acid H(CHB₁₁Cl₁₁) Stoyanov, Evgenii S.; Hoffmann, Stephan P.; Juhasz, Mark Journal of the American Chemical Society, Vol. 128, Issue 10 https://doi.org/10.1021/ja058581l	journal	February 2006
Hydrodefluorination and Other Hydrodehalogenation of Aliphatic Carbon−Halogen Bonds Using Silylium Catalysis Douvris, Christos; Nagaraja, C. M.; Chen, Chun-Hsing Journal of the American Chemical Society, Vol. 132, Issue 13 https://doi.org/10.1021/ja100605m	journal	March 2010
Rationalizing the Reactivity of Frustrated Lewis Pairs: Thermodynamics of H ₂ Activation and the Role of Acid−Base Properties Rokob, Tibor András; Hamza, Andrea; Pápai, Imre Journal of the American Chemical Society, Vol. 131, Issue 30 https://doi.org/10.1021/ja903878z	journal	August 2009
Carbon−Carbon Coupling of C(sp ³ )−F Bonds Using Alumenium Catalysis Gu, Weixing; Haneline, Mason R.; Douvris, Christos Journal of the American Chemical Society, Vol. 131, Issue 31 https://doi.org/10.1021/ja903927c	journal	August 2009
Thermochemical and Kinetic Study of the Carbocation Ring Contraction of Cyclohexylium to Methylcyclopentylium Mackie, Iain D.; Govindhakannan, Jagannathan; DiLabio, Gino A. The Journal of Physical Chemistry A, Vol. 112, Issue 17 https://doi.org/10.1021/jp710656f	journal	March 2008
Kinetic hydricity of transition-metal hydrides toward trityl cation Cheng, Tan-Yun; Bullock, R. Morris Organometallics, Vol. 14, Issue 9 https://doi.org/10.1021/om00009a001	journal	September 1995
Isolation, characterization and reactivity of three-coordinate phosphorus dications isoelectronic to alanes and silylium cations Mehlmann, Paul; Witteler, Tim; Wilm, Lukas F. B. Nature Chemistry, Vol. 11, Issue 12 https://doi.org/10.1038/s41557-019-0348-0	journal	October 2019
Structural characterization and reactivity of a room-temperature-stable, antiaromatic cyclopentadienyl cation salt Schulte, Yannick; Wölper, Christoph; Rupf, Susanne M. Nature Chemistry, Vol. 16, Issue 4 https://doi.org/10.1038/s41557-023-01417-5	journal	January 2024
Cationic silicon Lewis acids in catalysis Walker, Johannes C. L.; Klare, Hendrik F. T.; Oestreich, Martin Nature Reviews Chemistry, Vol. 4, Issue 1 https://doi.org/10.1038/s41570-019-0146-7	journal	November 2019
Convenient C-alkylation of the [HCB₁₁Cl₁₁]⁻carborane anion Ramírez-Contreras, Rodrigo; Ozerov, Oleg V. Dalton Trans., Vol. 41, Issue 26 https://doi.org/10.1039/C2DT12431A	journal	January 2012
Fluorocarbene, fluoroolefin, and fluorocarbyne complexes of Rh Pell, Christopher J.; Zhu, Yanjun; Huacuja, Rafael Chemical Science, Vol. 8, Issue 4 https://doi.org/10.1039/C6SC05391B	journal	January 2017
Isolable fluorinated triphenylmethyl cation salts of [HCB₁₁Cl₁₁]⁻: demonstration of remarkable hydride affinity Gunther, S. Olivia; Lee, Chun-I; Song, Ellen Chemical Science, Vol. 13, Issue 17 https://doi.org/10.1039/D1SC05936J	journal	January 2022
Towards clustered carbonyl cations [M₃(CO)₁₄]²⁺ (M = Ru, Os): the need for innocent deelectronation Sellin, Malte; Friedmann, Christian; Mayländer, Maximilian Chemical Science, Vol. 13, Issue 32 https://doi.org/10.1039/D2SC02358J	journal	January 2022
Tris(pentafluorophenyl)borane: a special boron Lewis acid for special reactions Erker, Gerhard Dalton Transactions, Issue 11 https://doi.org/10.1039/b503688g	journal	January 2005
Crystallographic Evidence for a Free Silylium Ion Kim, K. -C. Science, Vol. 297, Issue 5582 https://doi.org/10.1126/science.1073540	journal	August 2002
Hydrodefluorination of Perfluoroalkyl Groups Using Silylium-Carborane Catalysts Douvris, C.; Ozerov, O. V. Science, Vol. 321, Issue 5893 https://doi.org/10.1126/science.1159979	journal	August 2008

Similar Records

Abstraction of Hydride from Alkanes and Dihydrogen by the Perfluorotrityl Cation

Journal Article · 2025 · Angewandte Chemie (International Edition) · OSTI ID:2566935

Leong, Derek W.; Gogoi, Achyut R.; Maity, Tapas; +4 more

Chloride and Hydride Transfer as Keys to Catalytic Upcycling of Polyethylene into Liquid Alkanes

Journal Article · 2024 · Angewandte Chemie · OSTI ID:2324680

Zhang, Wei; Yao, Hai; Khare, Rachit; +12 more

Chloride and Hydride Transfer as Keys to Catalytic Upcycling of Polyethylene into Liquid Alkanes

Journal Article · 2024 · Angewandte Chemie (International Edition) · OSTI ID:2324697

Zhang, Wei; Yao, Hai; Khare, Rachit; +12 more

Title: Abstraction of Hydride from Alkanes and Dihydrogen by the Perfluorotrityl Cation

Citation Formats

References (40)

Similar Records

Related Subjects