Supported Lanthanum Borohydride Catalyzes CH Borylation Inside Zeolite Micropores

Li, Yuting; Kanbur, Uddhav; Cui, Jinlei; Wang, Guocang; Kobayashi, Takeshi; Sadow, Aaron D.; Qi, Long

doi:10.1002/ange.202117394

Title: Supported Lanthanum Borohydride Catalyzes CH Borylation Inside Zeolite Micropores

Journal Article · 17 February 2022 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202117394 · OSTI ID:1845726

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U.S. DOE Ames Laboratory Iowa State University Ames IA 50011 USA
U.S. DOE Ames Laboratory Iowa State University Ames IA 50011 USA, Department of Chemistry Iowa State University Ames IA 50011 USA

Abstract The zeolite‐supported lanthanide La(BH ₄ ) _x ‐HY ₃₀ catalyzes C−H borylation of benzene with pinacolborane (HBpin), providing a complementary approach to precious, late transition metal‐catalyzed borylations. The reactive catalytic species are generated from La grafted at the Brønsted acid sites (BAS) in micropores of the zeolite, whereas silanoate‐ and aluminoate‐grafted sites are inactive under the reaction conditions. During typical catalytic borylations, conversion to phenyl pinacolborane (PhBpin) is zero‐order in HBpin concentration. A turnover number (TON) of 167 is accessed by capping external silanols, selectively grafting at BAS sites, and adding HBpin slowly to the reaction.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1845726

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 15 Vol. 134; ISSN 0044-8249

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

Country of Publication:: Germany

Language:: English

References (40)

Bipyridine Periodic Mesoporous Organosilica: A Solid Ligand for the Iridium-Catalyzed Borylation of CH Bonds Grüning, Wolfram R.; Siddiqi, Georges; Safonova, Olga V. Advanced Synthesis & Catalysis, Vol. 356, Issue 4 https://doi.org/10.1002/adsc.201400125	journal	February 2014
Interconverting Lanthanum Hydride and Borohydride Catalysts for C=O Reduction and C−O Bond Cleavage Patnaik, Smita; Sadow, Aaron D. Angewandte Chemie, Vol. 131, Issue 8 https://doi.org/10.1002/ange.201813305	journal	January 2019
Catalytic Functionalization of Hydrocarbons by σ-Bond-Metathesis Chemistry: Dehydrosilylation of Methane with a Scandium Catalyst Sadow, Aaron D.; Tilley, T. Don Angewandte Chemie International Edition, Vol. 42, Issue 7 https://doi.org/10.1002/anie.200390213	journal	February 2003
Interconverting Lanthanum Hydride and Borohydride Catalysts for C=O Reduction and C−O Bond Cleavage Patnaik, Smita; Sadow, Aaron D. Angewandte Chemie International Edition, Vol. 58, Issue 8 https://doi.org/10.1002/anie.201813305	journal	February 2019
29Si NMR Shielding Tensors in Triphenylsilanes - 29Si Solid State NMR Experiments and DFT-IGLO Calculations Brendler, Erica; Heine, Thomas; Seichter, Wilhelm Zeitschrift für anorganische und allgemeine Chemie, Vol. 638, Issue 6 https://doi.org/10.1002/zaac.201200107	journal	May 2012
Borohydride complexes of rare earths, and their applications in various organic transformations Visseaux, Marc; Bonnet, Fanny Coordination Chemistry Reviews, Vol. 255, Issue 3-4 https://doi.org/10.1016/j.ccr.2010.09.016	journal	February 2011
Applications of Zeolites in Sustainable Chemistry Li, Yi; Li, Lin; Yu, Jihong Chem, Vol. 3, Issue 6 https://doi.org/10.1016/j.chempr.2017.10.009	journal	December 2017
Single-Site Cobalt-Catalyst Ligated with Pyridylimine-Functionalized Metal–Organic Frameworks for Arene and Benzylic Borylation Newar, Rajashree; Begum, Wahida; Antil, Neha Inorganic Chemistry, Vol. 59, Issue 15 https://doi.org/10.1021/acs.inorgchem.0c00747	journal	July 2020
Mechanistic Insights into C–H Borylation of Arenes with Organoiridium Catalysts Embedded in a Microporous Metal–Organic Framework Syed, Zoha H.; Chen, Zhihengyu; Idrees, Karam B. Organometallics, Vol. 39, Issue 7 https://doi.org/10.1021/acs.organomet.9b00874	journal	March 2020
Ortho -Selective C–H Borylation of Aromatic Ethers with Pinacol-borane by Organo Rare-Earth Catalysts Xue, Can; Luo, Yong; Teng, Huailong ACS Catalysis, Vol. 8, Issue 6 https://doi.org/10.1021/acscatal.8b01364	journal	April 2018
Organolanthanides in catalysis Watson, Patricia L.; Parshall, George W. Accounts of Chemical Research, Vol. 18, Issue 2 https://doi.org/10.1021/ar00110a004	journal	February 1985
Borylation and Silylation of C–H Bonds: A Platform for Diverse C–H Bond Functionalizations Hartwig, John F. Accounts of Chemical Research, Vol. 45, Issue 6 https://doi.org/10.1021/ar200206a	journal	November 2011
Facile, Metal-Mediated Dehydrogenative Borylation of Ethylene: Selective Conversion of a Titanium-Bound Olefin to a Vinylboronate Ester Motry, Douglas H.; Smith, Milton R. Journal of the American Chemical Society, Vol. 117, Issue 24 https://doi.org/10.1021/ja00129a035	journal	June 1995
.sigma.-Bond metathesis for carbon-hydrogen bonds of hydrocarbons and Sc-R (R = H, alkyl, aryl) bonds of permethylscandocene derivatives. Evidence for noninvolvement of the .pi. system in electrophilic activation of aromatic and vinylic C-H bonds Thompson, Mark E.; Baxter, Steven M.; Bulls, A. Ray Journal of the American Chemical Society, Vol. 109, Issue 1 https://doi.org/10.1021/ja00235a031	journal	January 1987
Carbon-hydrogen bond activating reactions of thoracyclobutanes. Routes to unusual actinide-transition metal .mu.-methylene complexes Smith, Gregory M.; Sabat, Michal; Marks, Tobin J. Journal of the American Chemical Society, Vol. 109, Issue 6 https://doi.org/10.1021/ja00240a042	journal	March 1987
Mild Iridium-Catalyzed Borylation of Arenes. High Turnover Numbers, Room Temperature Reactions, and Isolation of a Potential Intermediate Ishiyama, Tatsuo; Takagi, Jun; Ishida, Kousaku Journal of the American Chemical Society, Vol. 124, Issue 3 https://doi.org/10.1021/ja0173019	journal	January 2002
Synthesis and Characterization of Scandium Silyl Complexes of the Type Cp* ₂ ScSiHRR‘. σ-Bond Metathesis Reactions and Catalytic Dehydrogenative Silation of Hydrocarbons Sadow, Aaron D.; Tilley, T. Don Journal of the American Chemical Society, Vol. 127, Issue 2 https://doi.org/10.1021/ja040141r	journal	January 2005
A Solid Chelating Ligand: Periodic Mesoporous Organosilica Containing 2,2′-Bipyridine within the Pore Walls Waki, Minoru; Maegawa, Yoshifumi; Hara, Kenji Journal of the American Chemical Society, Vol. 136, Issue 10 https://doi.org/10.1021/ja4131609	journal	February 2014
Postsynthetic Metalation of Bipyridyl-Containing Metal–Organic Frameworks for Highly Efficient Catalytic Organic Transformations Manna, Kuntal; Zhang, Teng; Lin, Wenbin Journal of the American Chemical Society, Vol. 136, Issue 18 https://doi.org/10.1021/ja5018267	journal	April 2014
Bipyridine- and Phenanthroline-Based Metal–Organic Frameworks for Highly Efficient and Tandem Catalytic Organic Transformations via Directed C–H Activation Manna, Kuntal; Zhang, Teng; Greene, Francis X. Journal of the American Chemical Society, Vol. 137, Issue 7 https://doi.org/10.1021/ja512478y	journal	February 2015
Molecular Chemistry in a Zeolite: Genesis of a Zeolite Y-Supported Ruthenium Complex Catalyst Ogino, Isao; Gates, Bruce C. Journal of the American Chemical Society, Vol. 130, Issue 40 https://doi.org/10.1021/ja804265r	journal	October 2008
Iridium-Catalyzed sp ³ C–H Borylation in Hydrocarbon Solvent Enabled by 2,2′-Dipyridylarylmethane Ligands Jones, Margaret R.; Fast, Caleb D.; Schley, Nathan D. Journal of the American Chemical Society, Vol. 142, Issue 14 https://doi.org/10.1021/jacs.0c00524	journal	March 2020
Methane Borylation Catalyzed by Ru, Rh, and Ir Complexes in Comparison with Cyclohexane Borylation: Theoretical Understanding and Prediction Zhong, Rong-Lin; Sakaki, Shigeyoshi Journal of the American Chemical Society, Vol. 142, Issue 39 https://doi.org/10.1021/jacs.0c07239	journal	September 2020
Improving Stability of Zeolites in Aqueous Phase via Selective Removal of Structural Defects Prodinger, Sebastian; Derewinski, Miroslaw A.; Vjunov, Aleksei Journal of the American Chemical Society, Vol. 138, Issue 13 https://doi.org/10.1021/jacs.5b12785	journal	March 2016
Metal–Organic Framework Stabilizes a Low-Coordinate Iridium Complex for Catalytic Methane Borylation Feng, Xuanyu; Song, Yang; Li, Zhe Journal of the American Chemical Society, Vol. 141, Issue 28 https://doi.org/10.1021/jacs.9b04285	journal	June 2019
Silica-Supported Organolanthanum Catalysts for C–O Bond Cleavage in Epoxides Wang, Zhuoran; Patnaik, Smita; Eedugurala, Naresh Journal of the American Chemical Society, Vol. 142, Issue 6 https://doi.org/10.1021/jacs.9b11606	journal	January 2020
σ-Bond Metathesis: A 30-Year Retrospective Waterman, Rory Organometallics, Vol. 32, Issue 24 https://doi.org/10.1021/om400760k	journal	September 2013
Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes Manna, Kuntal; Ji, Pengfei; Lin, Zekai Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12610	journal	August 2016
Single-site trinuclear copper oxygen clusters in mordenite for selective conversion of methane to methanol Grundner, Sebastian; Markovits, Monica A. C.; Li, Guanna Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8546	journal	June 2015
Catalytic chemoselective functionalization of methane in a metal−organic framework Zhang, Xuan; Huang, Zhiyuan; Ferrandon, Magali Nature Catalysis, Vol. 1, Issue 5 https://doi.org/10.1038/s41929-018-0069-6	journal	May 2018
Supported neodymium catalysts for MMA polymerization: on the origin of surface-induced stereoselectivity Del Rosal, Iker; Tschan, Mathieu J. -L.; Gauvin, Régis M. Polym. Chem., Vol. 3, Issue 7 https://doi.org/10.1039/C2PY00472K	journal	January 2012
Iridium–bipyridine periodic mesoporous organosilica catalyzed direct C–H borylation using a pinacolborane Maegawa, Yoshifumi; Inagaki, Shinji Dalton Transactions, Vol. 44, Issue 29 https://doi.org/10.1039/C5DT00239G	journal	January 2015
Silanol defect engineering and healing in zeolites: opportunities to fine-tune their properties and performances Medeiros-Costa, Izabel C.; Dib, Eddy; Nesterenko, Nikolai Chemical Society Reviews, Vol. 50, Issue 19 https://doi.org/10.1039/D1CS00395J	journal	January 2021
Brnsted acidity of extraframework debris in steamed Y zeolites from the FTIR study of CO adsorption Cairon, Olivier; Chevreau, The´rèse; Lavalley, Jean-Claude Journal of the Chemical Society, Faraday Transactions, Vol. 94, Issue 19 https://doi.org/10.1039/a803886d	journal	January 1998
Cationic rare-earth metal bis(tetrahydridoborato) complexes: direct synthesis, structure and ring-opening polymerisation activity toward cyclic esters Robert, Dominique; Kondracka, Małgorzata; Okuda, Jun Dalton Transactions, Issue 20 https://doi.org/10.1039/b801030g	journal	January 2008
Polymerization of racemic β-butyrolactone using supported catalysts: a simple access to isotactic polymers Ajellal, Noureddine; Durieux, Guillaume; Delevoye, Laurent Chemical Communications, Vol. 46, Issue 7 https://doi.org/10.1039/b923546a	journal	January 2010
Remarkably Selective Iridium Catalysts for the Elaboration of Aromatic C-H Bonds Cho, J. -Y. Science, Vol. 295, Issue 5553 https://doi.org/10.1126/science.1067074	journal	November 2001
Catalytic Cleavage of the C-H and C-C Bonds of Alkanes by Surface Organometallic Chemistry: An EXAFS and IR Characterization of a Zr-H Catalyst Corker, J.; Lefebvre, F. d. r.; Evans, J. Science, Vol. 271, Issue 5251 https://doi.org/10.1126/science.271.5251.966	journal	February 1996
Catalyst-controlled selectivity in the C-H borylation of methane and ethane Cook, A. K.; Schimler, S. D.; Matzger, A. J. Science, Vol. 351, Issue 6280 https://doi.org/10.1126/science.aad9289	journal	March 2016
Catalytic borylation of methane Smith, K. T.; Berritt, S.; Gonzalez-Moreiras, M. Science, Vol. 351, Issue 6280 https://doi.org/10.1126/science.aad9730	journal	March 2016

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