The Critical Role of Reductive Steps in the Nickel‐Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C−O Bonds
Abstract
The hydrogenolysis of the aromatic C-O bond in aryl ethers catalyzed by Ni was studied in decalin and water. Observations of a significant kinetic isotope effect (kH/kD=5.7) for the reactions of diphenyl ether under H2 and D2 atmosphere and a positive dependence of the rate on H2 chemical potential in decalin indicate that addition of H to the aromatic ring is involved in the rate-limiting step. All kinetic evidence points to the fact that H addition occurs concerted with C-O bond scission. DFT calculations also suggest a route consistent with these observations involving hydrogen atom addition to the ipso position of the phenyl ring concerted with C-O scission. Hydrogenolysis initiated by H addition in water is more selective (ca. 75 %) than reactions in decalin (ca. 30 %).
- Authors:
-
[1];
[1];
[1];
[4]
- Institute for Integrated Catalysis Pacific Northwest National Laboratory P.O. Box 999 Richland WA 99352 USA
- School of Chemical Engineering and Technology Tianjin University Tianjin 300072 China
- School of Chemistry and Chemical Engineering Tianjin Polytechnic University Tianjin 300387 China
- Institute for Integrated Catalysis Pacific Northwest National Laboratory P.O. Box 999 Richland WA 99352 USA, Department of Chemistry and Catalysis Research Institute TU München Lichtenbergstrasse 4 85748 Garching Germany
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1605477
- Alternate Identifier(s):
- OSTI ID: 1605478; OSTI ID: 1623490
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Published Article
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition) Journal Volume: 59 Journal Issue: 4; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley Blackwell (John Wiley & Sons)
- Country of Publication:
- Germany
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Chemistry
Citation Formats
Wang, Meng, Zhao, Yuntao, Mei, Donghai, Bullock, R. Morris, Gutiérrez, Oliver Y., Camaioni, Donald M., and Lercher, Johannes A. The Critical Role of Reductive Steps in the Nickel‐Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C−O Bonds. Germany: N. p., 2019.
Web. doi:10.1002/anie.201909551.
Wang, Meng, Zhao, Yuntao, Mei, Donghai, Bullock, R. Morris, Gutiérrez, Oliver Y., Camaioni, Donald M., & Lercher, Johannes A. The Critical Role of Reductive Steps in the Nickel‐Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C−O Bonds. Germany. https://doi.org/10.1002/anie.201909551
Wang, Meng, Zhao, Yuntao, Mei, Donghai, Bullock, R. Morris, Gutiérrez, Oliver Y., Camaioni, Donald M., and Lercher, Johannes A. Thu .
"The Critical Role of Reductive Steps in the Nickel‐Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C−O Bonds". Germany. https://doi.org/10.1002/anie.201909551.
@article{osti_1605477,
title = {The Critical Role of Reductive Steps in the Nickel‐Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C−O Bonds},
author = {Wang, Meng and Zhao, Yuntao and Mei, Donghai and Bullock, R. Morris and Gutiérrez, Oliver Y. and Camaioni, Donald M. and Lercher, Johannes A.},
abstractNote = {The hydrogenolysis of the aromatic C-O bond in aryl ethers catalyzed by Ni was studied in decalin and water. Observations of a significant kinetic isotope effect (kH/kD=5.7) for the reactions of diphenyl ether under H2 and D2 atmosphere and a positive dependence of the rate on H2 chemical potential in decalin indicate that addition of H to the aromatic ring is involved in the rate-limiting step. All kinetic evidence points to the fact that H addition occurs concerted with C-O bond scission. DFT calculations also suggest a route consistent with these observations involving hydrogen atom addition to the ipso position of the phenyl ring concerted with C-O scission. Hydrogenolysis initiated by H addition in water is more selective (ca. 75 %) than reactions in decalin (ca. 30 %).},
doi = {10.1002/anie.201909551},
journal = {Angewandte Chemie (International Edition)},
number = 4,
volume = 59,
place = {Germany},
year = {2019},
month = {12}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/anie.201909551
https://doi.org/10.1002/anie.201909551
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 27 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Nickel-Mediated Hydrogenolysis of C–O Bonds of Aryl Ethers: What Is the Source of the Hydrogen?
journal, March 2012
- Kelley, Paul; Lin, Sibo; Edouard, Guy
- Journal of the American Chemical Society, Vol. 134, Issue 12, p. 5480-5483
Mild Continuous Hydrogenolysis of Kraft Lignin over Titanium Nitride–Nickel Catalyst
journal, February 2016
- Molinari, Valerio; Clavel, Guylhaine; Graglia, Micaela
- ACS Catalysis, Vol. 6, Issue 3
Palladium-Catalyzed Formal Cross-Coupling of Diaryl Ethers with Amines: Slicing the 4- O -5 Linkage in Lignin Models
journal, March 2018
- Zeng, Huiying; Cao, Dawei; Qiu, Zihang
- Angewandte Chemie International Edition, Vol. 57, Issue 14
Nickel-Catalyzed Cross-Couplings Involving Carbon−Oxygen Bonds
journal, March 2011
- Rosen, Brad M.; Quasdorf, Kyle W.; Wilson, Daniella A.
- Chemical Reviews, Vol. 111, Issue 3
Synthesis of ketones from biomass-derived feedstock
journal, January 2017
- Meng, Qinglei; Hou, Minqiang; Liu, Huizhen
- Nature Communications, Vol. 8, Issue 1
Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds
journal, March 2018
- Wang, Meng; Gutiérrez, Oliver Y.; Camaioni, Donald M.
- Angewandte Chemie International Edition, Vol. 57, Issue 14
Efficient cleavage of aryl ether C–O linkages by Rh–Ni and Ru–Ni nanoscale catalysts operating in water
journal, January 2018
- Bulut, Safak; Siankevich, Sviatlana; van Muyden, Antoine P.
- Chemical Science, Vol. 9, Issue 25
A Heterogeneous Nickel Catalyst for the Hydrogenolysis of Aryl Ethers without Arene Hydrogenation
journal, December 2012
- Sergeev, Alexey G.; Webb, Jonathan D.; Hartwig, John F.
- Journal of the American Chemical Society, Vol. 134, Issue 50, p. 20226-20229
Formic-acid-induced depolymerization of oxidized lignin to aromatics
journal, November 2014
- Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J.
- Nature, Vol. 515, Issue 7526, p. 249-252
Hydrogenation and Hydrogenolysis of Ethers
journal, January 1935
- Duzee, Edward M. van; Adkins, Homer
- Journal of the American Chemical Society, Vol. 57, Issue 1
Bright Side of Lignin Depolymerization: Toward New Platform Chemicals
journal, January 2018
- Sun, Zhuohua; Fridrich, Bálint; de Santi, Alessandra
- Chemical Reviews, Vol. 118, Issue 2
On the structure sensitivity of ethane hydrogenolysis on Ni catalysts
journal, November 1979
- Sárkány, A.; Tétényi, P.
- Reaction Kinetics and Catalysis Letters, Vol. 12, Issue 3
Lignin Valorizations with Ni Catalysts for Renewable Chemicals and Fuels Productions
journal, May 2019
- Chen, Xiao; Guan, Weixiang; Tsang, Chi-Wing
- Catalysts, Vol. 9, Issue 6
Mechanisms of catalytic cleavage of benzyl phenyl ether in aqueous and apolar phases
journal, March 2014
- He, Jiayue; Lu, Lu; Zhao, Chen
- Journal of Catalysis, Vol. 311
Ni-Catalyzed Cleavage of Aryl Ethers in the Aqueous Phase
journal, December 2012
- He, Jiayue; Zhao, Chen; Lercher, Johannes A.
- Journal of the American Chemical Society, Vol. 134, Issue 51, p. 20768-20775
Chemo- and Regioselective Hydrogenolysis of Diaryl Ether C−O Bonds by a Robust Heterogeneous Ni/C Catalyst: Applications to the Cleavage of Complex Lignin-Related Fragments
journal, December 2015
- Gao, Fang; Webb, Jonathan D.; Hartwig, John F.
- Angewandte Chemie International Edition, Vol. 55, Issue 4
Catalytic Hydrogenolysis of Aryl Ethers: A Key Step in Lignin Valorization to Valuable Chemicals
journal, February 2015
- Zaheer, Muhammad; Kempe, Rhett
- ACS Catalysis, Vol. 5, Issue 3
The Catalytic Valorization of Lignin for the Production of Renewable Chemicals
journal, June 2010
- Zakzeski, Joseph; Bruijnincx, Pieter C. A.; Jongerius, Anna L.
- Chemical Reviews, Vol. 110, Issue 6, p. 3552-3599
Palladium-Catalyzed Hydrolytic Cleavage of Aromatic C−O Bonds
journal, January 2017
- Wang, Meng; Shi, Hui; Camaioni, Donald M.
- Angewandte Chemie, Vol. 129, Issue 8
Integrating lignin valorization and bio-ethanol production: on the role of Ni-Al 2 O 3 catalyst pellets during lignin-first fractionation
journal, January 2017
- Van den Bosch, S.; Renders, T.; Kennis, S.
- Green Chemistry, Vol. 19, Issue 14
Rh nanoparticles with NiO x surface decoration for selective hydrogenolysis of C O bond over arene hydrogenation
journal, October 2016
- Zhang, Jiaguang; Ibrahim, Mahmoud; Collière, Vincent
- Journal of Molecular Catalysis A: Chemical, Vol. 422
Selective, Nickel-Catalyzed Hydrogenolysis of Aryl Ethers
journal, April 2011
- Sergeev, A. G.; Hartwig, J. F.
- Science, Vol. 332, Issue 6028, p. 439-443
Solvent Effects on the Hydrogenolysis of Diphenyl Ether with Raney Nickel and their Implications for the Conversion of Lignin
journal, April 2012
- Wang, Xingyu; Rinaldi, Roberto
- ChemSusChem, Vol. 5, Issue 8, p. 1455-1466
Palladium-Catalyzed Formal Cross-Coupling of Diaryl Ethers with Amines: Slicing the 4- O -5 Linkage in Lignin Models
journal, March 2018
- Zeng, Huiying; Cao, Dawei; Qiu, Zihang
- Angewandte Chemie, Vol. 130, Issue 14
Support effects in hydrogenation of cinnamaldehyde over carbon nanofiber-supported platinum catalysts: Kinetic modeling
journal, November 2005
- Toebes, Marjolein L.; Alexander Nijhuis, T.; Hájek, Jan
- Chemical Engineering Science, Vol. 60, Issue 21
Solvent-mediated charge separation drives alternative hydrogenation path of furanics in liquid water
journal, April 2019
- Zhao, Zheng; Bababrik, Reda; Xue, Wenhua
- Nature Catalysis, Vol. 2, Issue 5
Metal-catalyzed activation of ethers via C–O bond cleavage: a new strategy for molecular diversity
journal, January 2014
- Cornella, Josep; Zarate, Cayetana; Martin, Ruben
- Chem. Soc. Rev., Vol. 43, Issue 23
Chemo- and Regioselective Hydrogenolysis of Diaryl Ether C−O Bonds by a Robust Heterogeneous Ni/C Catalyst: Applications to the Cleavage of Complex Lignin-Related Fragments
journal, December 2015
- Gao, Fang; Webb, Jonathan D.; Hartwig, John F.
- Angewandte Chemie, Vol. 128, Issue 4
Mechanistic Investigations of the Hydrogenolysis of Diaryl Ethers Catalyzed by Nickel Complexes of N -Heterocyclic Carbene Ligands
journal, November 2017
- Saper, Noam I.; Hartwig, John F.
- Journal of the American Chemical Society, Vol. 139, Issue 48
Combined Experimental and Theoretical Study on the Reductive Cleavage of Inert C–O Bonds with Silanes: Ruling out a Classical Ni(0)/Ni(II) Catalytic Couple and Evidence for Ni(I) Intermediates
journal, January 2013
- Cornella, Josep; Gómez-Bengoa, Enrique; Martin, Ruben
- Journal of the American Chemical Society, Vol. 135, Issue 5
Palladium-Catalyzed Reductive Insertion of Alcohols into Aryl Ether Bonds
journal, March 2018
- Wang, Meng; Gutiérrez, Oliver Y.; Camaioni, Donald M.
- Angewandte Chemie, Vol. 130, Issue 14
Ni-Catalyzed Reduction of Inert C−O Bonds: A New Strategy for Using Aryl Ethers as Easily Removable Directing Groups
journal, December 2010
- Álvarez-Bercedo, Paula; Martin, Ruben
- Journal of the American Chemical Society, Vol. 132, Issue 49
Bimetallic catalysts for upgrading of biomass to fuels and chemicals
journal, January 2012
- Alonso, David Martin; Wettstein, Stephanie G.; Dumesic, James A.
- Chemical Society Reviews, Vol. 41, Issue 24, p. 8075-8098
Catalytic hydrogenation of cyclohexene 7. Liquid phase reaction on supported nickel
journal, July 1987
- Boudart, M.
- Journal of Catalysis, Vol. 106, Issue 1
Palladium-Catalyzed Hydrolytic Cleavage of Aromatic C−O Bonds
journal, January 2017
- Wang, Meng; Shi, Hui; Camaioni, Donald M.
- Angewandte Chemie International Edition, Vol. 56, Issue 8