Surface Protected Organozirconium Catalyzes C─H Alumination of Saturated Hydrocarbons

Banerjee, Sayak; Rodriguez, Jessica; Mais, Marco; Perras, Frédéric A.; Sadow, Aaron D.

doi:10.1002/anie.202511893

Surface Protected Organozirconium Catalyzes C─H Alumination of Saturated Hydrocarbons

Journal Article · Tue Jul 08 00:00:00 UTC 2025 · Angewandte Chemie International Edition

DOI:https://doi.org/10.1002/anie.202511893· OSTI ID:2586712

^[1]; Rodriguez, Jessica ^[1]; Mais, Marco ^[1]; ^[1]; ^[1]

Iowa State Univ., Ames, IA (United States); Ames Laboratory (AMES), Ames, IA (United States)

Surface grafted organozirconium catalyzes C─H/Et─Al exchange reactions, involving saturated hydrocarbons and AlEt₃, to afford organoaluminum compounds and ethane. The Zr(O^tBu)₃@SiO₂-Al₂O₃_–700 (1) catalyst contains monopodal ≡SiO─Zr(O^tBu)₃ and only a few residual silanols (<5%). Nonetheless, these silanols are the Achille's heel of 1, providing a pathway for surface and catalyst degradation during catalysis, limiting the alkylaluminum yield and catalyst turnover. Support degradation, involving the cleavage of Si─O bonds by activated surface organometallics, is inhibited by capping silanols with ─SiMe₃. Residual silanols in 1 react with allyltrimethylsilane, as determined by solid-state ¹³C and ²⁹Si nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy, and reaction stoichiometry, to form Zr(O^tBu)₃/SiMe₃@SiO₂-Al₂O_3–700 (2), which is resistant to degradation by AlEt₃. C─H alumination of dodecane catalyzed by 2 produces higher yields of the 1-dodecylaluminum product in comparison to 1, and in >95% selectivity. Additionally, methane undergoes 2-catalyzed C─H alumination, providing a route to AlMe₃.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 2586712

Journal Information:: Angewandte Chemie International Edition, Journal Name: Angewandte Chemie International Edition Journal Issue: 36 Vol. 64; ISSN 1521-3773; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (46)

Catalytic Hydrogenolysis at Low Temperature and Pressure of Polyethylene and Polypropylene to Diesels or Lower Alkanes by a Zirconium Hydride Supported on Silica-Alumina: A Step Toward Polyolefin Degradation by the Microscopic Reverse of Ziegler-Natta Polymerization Dufaud, Véronique; Basset, Jean-Marie Angewandte Chemie International Edition, Vol. 37, Issue 6 https://doi.org/10.1002/(SICI)1521-3773(19980403)37:6<806::AID-ANIE806>3.0.CO;2-6	journal	April 1998
Surface Organometallic Chemistry on Oxides: Selective Catalytic Low-Temperature Hydrogenolysis of Alkanes by a Highly Electrophilic Zirconium Hydride Complex Supported on Silica Lecuyer, Christine; Quignard, Francoise; Choplin, Agnès Angewandte Chemie International Edition in English, Vol. 30, Issue 12 https://doi.org/10.1002/anie.199116601	journal	December 1991
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
Homologation of Propane Catalyzed by Oxide-Supported Zirconium Dihydride and Dialkyl Complexes Thieuleux, Chloé; Maraval, Alexandrine; Veyre, Laurent Angewandte Chemie International Edition, Vol. 46, Issue 13 https://doi.org/10.1002/anie.200604158	journal	March 2007
Tuning the Selectivity of Alumina-Supported (CH3)ReO3 by Modifying the Surface Properties of the Support Salameh, Alain; Baudouin, Anne; Basset, Jean-Marie Angewandte Chemie International Edition, Vol. 47, Issue 11 https://doi.org/10.1002/anie.200704876	journal	February 2008
Scandium‐Catalyzed Silylation of Aromatic CH Bonds Oyamada, Juzo; Nishiura, Masayoshi; Hou, Zhaomin Angewandte Chemie International Edition, Vol. 50, Issue 45 https://doi.org/10.1002/anie.201105636	journal	September 2011
Palladium‐Catalyzed Carbon–Fluorine and Carbon–Hydrogen Bond Alumination of Fluoroarenes and Heteroarenes Chen, Wenyi; Hooper, Thomas N.; Ng, Jamues Angewandte Chemie International Edition, Vol. 56, Issue 41 https://doi.org/10.1002/anie.201706378	journal	August 2017
Activation of C−F Bonds by Electrophilic Organosilicon Sites Supported on Sulfated Zirconia Culver, Damien B.; Conley, Matthew P. Angewandte Chemie International Edition, Vol. 57, Issue 45 https://doi.org/10.1002/anie.201809199	journal	October 2018
Supported Lanthanum Borohydride Catalyzes CH Borylation Inside Zeolite Micropores Li, Yuting; Kanbur, Uddhav; Cui, Jinlei Angewandte Chemie International Edition, Vol. 61, Issue 15 https://doi.org/10.1002/anie.202117394	journal	February 2022
Yttrium‐Catalyzed ortho‐Selective C−H Borylation of Pyridines with Pinacolborane Luo, Yuncong; Jiang, Shengjie; Xu, Xin Angewandte Chemie International Edition, Vol. 61, Issue 21 https://doi.org/10.1002/anie.202117750	journal	March 2022
Effect of Support on Metathesis of n‐Decane: Drastic Improvement in Alkane Metathesis with WMe₅ Linked to Silica–Alumina Samantaray, Manoja K.; Dey, Raju; Abou‐Hamad, Edy Chemistry – A European Journal, Vol. 21, Issue 16, p. 6100-6106 https://doi.org/10.1002/chem.201406033	journal	March 2015
Cationic group IV metal alkyl complexes and their role as olefin polymerization catalysts: The formation of ethyl-bridged dinuclear and heterodinuclear zirconium and hafnium complexes Bochmann, Manfred; Lancaster, Simon J. Journal of Organometallic Chemistry, Vol. 497, Issue 1-2, p. 55-59 https://doi.org/10.1016/0022-328X(95)00109-4	journal	July 1995
Surface organometallic chemistry of zirconium: Application to the stoichiometric activation of the CH bonds of alkanes and to the low-temperature catalytic hydrogenolysis of alkanes Quignard, Françoise; Le´cuyer, Christine; Choplin, Agne`s Journal of Molecular Catalysis, Vol. 74, Issue 1-3 https://doi.org/10.1016/0304-5102(92)80253-D	journal	July 1992
Zirconocene catalysts for olefin polymerization Kaminsky, W. Catalysis Today, Vol. 20, Issue 2 https://doi.org/10.1016/0920-5861(94)80005-7	journal	June 1994
Synthesis of trimethylaluminium Pasynkiewicz, S.; Boleslawski, M. Journal of Organometallic Chemistry, Vol. 25, Issue 1 https://doi.org/10.1016/S0022-328X(00)86201-4	journal	November 1970
Catalytic carbon-carbon bond cleavage and carbon-element bond formation give new life for polyolefins as biodegradable surfactants Kanbur, Uddhav; Zang, Guiyan; Paterson, Alexander L. Chem, Vol. 7, Issue 5 https://doi.org/10.1016/j.chempr.2021.03.007	journal	May 2021
Zirconium-Catalyzed Asymmetric Carboalumination of Unactivated Terminal Alkenes Xu, Shiqing; Negishi, Ei-ichi Accounts of Chemical Research, Vol. 49, Issue 10 https://doi.org/10.1021/acs.accounts.6b00338	journal	September 2016
Determining the Three-Dimensional Structures of Silica-Supported Metal Complexes from the Ground Up Perras, Frédéric A.; Kanbur, Uddhav; Paterson, Alexander L. Inorganic Chemistry, Vol. 61, Issue 2 https://doi.org/10.1021/acs.inorgchem.1c03200	journal	December 2021
Supported Electrophilic Organoruthenium Catalyst for the Hydrosilylation of Olefins Kanbur, Uddhav; Witzke, Ryan J.; Xu, Jiayi ACS Catalysis, Vol. 13, Issue 20 https://doi.org/10.1021/acscatal.3c03399	journal	October 2023
Enhanced Activity from Coordinatively Unsaturated and Dynamic Zeolite-Bound Organoscandium Species Southern, Scott A.; Li, Yuting; Liu, Da-Jiang ACS Catalysis, Vol. 14, Issue 12, p. 9440-9451 https://doi.org/10.1021/acscatal.4c00678	journal	June 2024
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
Mesostructured Hybrid Organic–Silica Materials: Ideal Supports for Well-Defined Heterogeneous Organometallic Catalysts Conley, Matthew P.; Copéret, Christophe; Thieuleux, Chloé ACS Catalysis, Vol. 4, Issue 5 https://doi.org/10.1021/cs500262t	journal	April 2014
Zirconium-catalyzed coupling of propene and .alpha.-picoline Jordan, Richard F.; Taylor, Dennis F. Journal of the American Chemical Society, Vol. 111, Issue 2 https://doi.org/10.1021/ja00184a081	journal	January 1989
.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
Methane exchange reactions of lanthanide and early-transition-metal methyl complexes Watson, Patricia L. Journal of the American Chemical Society, Vol. 105, Issue 21 https://doi.org/10.1021/ja00359a023	journal	October 1983
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
Rare-Earth-Catalyzed C–H Bond Addition of Pyridines to Olefins Guan, Bing-Tao; Hou, Zhaomin Journal of the American Chemical Society, Vol. 133, Issue 45 https://doi.org/10.1021/ja208129t	journal	October 2011
Nature and Structure of Aluminum Surface Sites Grafted on Silica from a Combination of High-Field Aluminum-27 Solid-State NMR Spectroscopy and First-Principles Calculations Kerber, Rachel Nathaniel; Kermagoret, Anthony; Callens, Emmanuel Journal of the American Chemical Society, Vol. 134, Issue 15 https://doi.org/10.1021/ja3008566	journal	April 2012
Hydrophobic Zeolites for Biofuel Upgrading Reactions at the Liquid–Liquid Interface in Water/Oil Emulsions Zapata, Paula A.; Faria, Jimmy; Ruiz, M. Pilar Journal of the American Chemical Society, Vol. 134, Issue 20 https://doi.org/10.1021/ja3015082	journal	May 2012
Evidence for Metal–Surface Interactions and Their Role in Stabilizing Well-Defined Immobilized Ru–NHC Alkene Metathesis Catalysts Samantaray, Manoja K.; Alauzun, Johan; Gajan, David Journal of the American Chemical Society, Vol. 135, Issue 8 https://doi.org/10.1021/ja311722k	journal	February 2013
Kinetics and Mechanism of Olefin Epoxidation with Aqueous H ₂ O ₂ and a Highly Selective Surface-Modified TaSBA15 Heterogeneous Catalyst Ruddy, Daniel A.; Tilley, T. Don Journal of the American Chemical Society, Vol. 130, Issue 33 https://doi.org/10.1021/ja8027313	journal	August 2008
Catalytic Hydrogenolysis and Isomerization of Light Alkanes over the Silica-Supported Titanium Hydride Complex (⋮SiO) ₃ TiH Rosier, Cécile; Niccolai, Gerald P.; Basset, Jean-Marie Journal of the American Chemical Society, Vol. 119, Issue 50 https://doi.org/10.1021/ja972488i	journal	December 1997
Chemodivergent Organolanthanide-Catalyzed C–H α-Mono-Borylation of Pyridines Rothbaum, Jacob O.; Motta, Alessandro; Kratish, Yosi Journal of the American Chemical Society, Vol. 144, Issue 37 https://doi.org/10.1021/jacs.2c06844	journal	September 2022
Zirconium-Catalyzed C–H Alumination of Polyolefins, Paraffins, and Methane Kanbur, Uddhav; Paterson, Alexander L.; Rodriguez, Jessica Journal of the American Chemical Society, Vol. 145, Issue 5 https://doi.org/10.1021/jacs.2c11056	journal	January 2023
Silica Supported Organometallic Ir^I Complexes Enable Efficient Catalytic Methane Borylation Staples, Orion; Ferrandon, Magali S.; Laurent, Guillaume P. Journal of the American Chemical Society, Vol. 145, Issue 14, p. 7992-8000 https://doi.org/10.1021/jacs.2c13612	journal	March 2023
Trimethylaluminum Activates Zeolite-Confined Lanthanum Borohydrides to Enhance Catalytic C–H Borylation Li, Yuting; Kobayashi, Takeshi; Meira, Debora M. Journal of the American Chemical Society, Vol. 147, Issue 15 https://doi.org/10.1021/jacs.4c18569	journal	April 2025
Influence of Surface Modification of Ti−SBA15 Catalysts on the Epoxidation Mechanism for Cyclohexene with Aqueous Hydrogen Peroxide Brutchey, Richard L.; Ruddy, Daniel A.; Andersen, Lars K. Langmuir, Vol. 21, Issue 21 https://doi.org/10.1021/la051182j	journal	October 2005
Mechanistic Investigation on Scandium-Catalyzed C–H Addition of Pyridines to Olefins Luo, Gen; Luo, Yi; Qu, Jingping Organometallics, Vol. 31, Issue 10 https://doi.org/10.1021/om300147y	journal	May 2012
σ-Bond Metathesis: A 30-Year Retrospective Waterman, Rory Organometallics, Vol. 32, Issue 24 https://doi.org/10.1021/om400760k	journal	September 2013
Methane activation by silica-supported Zr( iv ) hydrides: the dihydride [(SiO) ₂ ZrH ₂ ] is much faster than the monohydride [(SiO) ₃ ZrH] Thieuleux, Chloé; Quadrelli, Elsje Alessandra; Basset, Jean-Marie Chem. Commun., Issue 15 https://doi.org/10.1039/B404749D	journal	January 2004
Facile C–H activation by lutetium–methyl and lutetium–hydride complexes Watson, Patricia L. J. Chem. Soc., Chem. Commun., Issue 6 https://doi.org/10.1039/C39830000276	journal	January 1983
Room temperature catalytic carbon–hydrogen bond alumination of unactivated arenes: mechanism and selectivity Hooper, Thomas N.; Garçon, Martí; White, Andrew J. P. Chemical Science, Vol. 9, Issue 24 https://doi.org/10.1039/C8SC02072H	journal	January 2018
Al(OR ^F ) ₃ (R ^F = C(CF ₃ ) ₃ ) activated silica: a well-defined weakly coordinating surface anion Culver, Damien B.; Venkatesh, Amrit; Huynh, Winn Chemical Science, Vol. 11, Issue 6 https://doi.org/10.1039/C9SC05904K	journal	January 2020
A comparative IR characterization of acidic sites on HY zeolite by pyridine and CO probes with silica–alumina and γ-alumina references Kondo, Junko N.; Nishitani, Ryoko; Yoda, Eisuke Physical Chemistry Chemical Physics, Vol. 12, Issue 37 https://doi.org/10.1039/c0cp00203h	journal	January 2010
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
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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