Revealing the Configuration and Conformation of Surface Organometallic Catalysts with DNP-Enhanced NMR
Abstract
Although single-site, supported organometallic catalysts were designed with homogeneity in mind, little is strictly known about their atomic-level structure and uniformity. This is in large part due to the inability of conventional characterization tools to provide structural information with adequate resolution and range for this purpose. In this work, we show that dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (NMR) enables the measurement of distances between the surface and individual carbons, making it possible to orient complexes and molecules on surfaces. We use this approach to determine the orientation and configuration of naturally 13C-abundant acetate and supported organoiridium(III) pincer complex, both supported on γ-Al2O3. By combining solid-state NMR and extended X-ray absorption fine structure spectroscopy (EXAFS) experiments with periodic density functional theory (DFT) calculations, we are able to determine the three-dimensional arrangement of ligands around the metal center and thereby identify the structure of the supported complex at a resolution reminiscent of that associated with single-crystal diffractometry.
- Authors:
-
- Ames Lab., Ames, IA (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
- OSTI Identifier:
- 1798866
- Alternate Identifier(s):
- OSTI ID: 1831741
- Report Number(s):
- IS-J-10,522
Journal ID: ISSN 1932-7447
- Grant/Contract Number:
- AC-02-07CH11358; DGE-1842165; AC-02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 125; Journal Issue: 24; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemical structure; oxides; organic compounds; transition metals; ligands
Citation Formats
Perras, Frédéric A., Paterson, Alexander L., Syed, Zoha H., Kropf, A. Jeremy, Kaphan, David M., Delferro, Massimiliano, and Pruski, Marek. Revealing the Configuration and Conformation of Surface Organometallic Catalysts with DNP-Enhanced NMR. United States: N. p., 2021.
Web. doi:10.1021/acs.jpcc.1c03176.
Perras, Frédéric A., Paterson, Alexander L., Syed, Zoha H., Kropf, A. Jeremy, Kaphan, David M., Delferro, Massimiliano, & Pruski, Marek. Revealing the Configuration and Conformation of Surface Organometallic Catalysts with DNP-Enhanced NMR. United States. https://doi.org/10.1021/acs.jpcc.1c03176
Perras, Frédéric A., Paterson, Alexander L., Syed, Zoha H., Kropf, A. Jeremy, Kaphan, David M., Delferro, Massimiliano, and Pruski, Marek. Fri .
"Revealing the Configuration and Conformation of Surface Organometallic Catalysts with DNP-Enhanced NMR". United States. https://doi.org/10.1021/acs.jpcc.1c03176. https://www.osti.gov/servlets/purl/1798866.
@article{osti_1798866,
title = {Revealing the Configuration and Conformation of Surface Organometallic Catalysts with DNP-Enhanced NMR},
author = {Perras, Frédéric A. and Paterson, Alexander L. and Syed, Zoha H. and Kropf, A. Jeremy and Kaphan, David M. and Delferro, Massimiliano and Pruski, Marek},
abstractNote = {Although single-site, supported organometallic catalysts were designed with homogeneity in mind, little is strictly known about their atomic-level structure and uniformity. This is in large part due to the inability of conventional characterization tools to provide structural information with adequate resolution and range for this purpose. In this work, we show that dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (NMR) enables the measurement of distances between the surface and individual carbons, making it possible to orient complexes and molecules on surfaces. We use this approach to determine the orientation and configuration of naturally 13C-abundant acetate and supported organoiridium(III) pincer complex, both supported on γ-Al2O3. By combining solid-state NMR and extended X-ray absorption fine structure spectroscopy (EXAFS) experiments with periodic density functional theory (DFT) calculations, we are able to determine the three-dimensional arrangement of ligands around the metal center and thereby identify the structure of the supported complex at a resolution reminiscent of that associated with single-crystal diffractometry.},
doi = {10.1021/acs.jpcc.1c03176},
journal = {Journal of Physical Chemistry. C},
number = 24,
volume = 125,
place = {United States},
year = {Fri Jun 11 00:00:00 EDT 2021},
month = {Fri Jun 11 00:00:00 EDT 2021}
}
Works referenced in this record:
Structural models of activated γ-alumina surfaces revisited: Thermodynamics, NMR and IR spectroscopies from ab initio calculations
journal, September 2013
- Ferreira, Ary R.; Küçükbenli, Emine; de Gironcoli, Stefano
- Chemical Physics, Vol. 423
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
Molecular design of heterogeneous catalysts: the case of olefin metathesis
journal, January 2004
- Copéret, Christophe
- New J. Chem., Vol. 28, Issue 1
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Observing the three-dimensional dynamics of supported metal complexes
journal, January 2021
- Paterson, Alexander L.; Liu, Da-Jiang; Kanbur, Uddhav
- Inorganic Chemistry Frontiers, Vol. 8, Issue 6
Catalysis and Surface Organometallic Chemistry: A View from Theory and Simulations
journal, March 2010
- Sautet, Philippe; Delbecq, Françoise
- Chemical Reviews, Vol. 110, Issue 3
Local Structures and Heterogeneity of Silica-Supported M(III) Sites Evidenced by EPR, IR, NMR, and Luminescence Spectroscopies
journal, June 2017
- Delley, Murielle F.; Lapadula, Giuseppe; Núñez-Zarur, Francisco
- Journal of the American Chemical Society, Vol. 139, Issue 26
Relaxation of Crystals with the Quasi-Newton Method
journal, February 1997
- Pfrommer, Bernd G.; Côté, Michel; Louie, Steven G.
- Journal of Computational Physics, Vol. 131, Issue 1
Measurement of Aluminum-Carbon Distances Using S-RESPDOR NMR Experiments
journal, September 2012
- Pourpoint, Frédérique; Trébosc, Julien; Gauvin, Régis M.
- ChemPhysChem, Vol. 13, Issue 16
Characterizing Substrate–Surface Interactions on Alumina-Supported Metal Catalysts by Dynamic Nuclear Polarization-Enhanced Double-Resonance NMR Spectroscopy
journal, February 2017
- Perras, Frédéric A.; Padmos, J. Daniel; Johnson, Robert L.
- Journal of the American Chemical Society, Vol. 139, Issue 7
Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009
- Tkatchenko, Alexandre; Scheffler, Matthias
- Physical Review Letters, Vol. 102, Issue 7
Measuring multiple carbon–nitrogen distances in natural abundant solids using R-RESPDOR NMR
journal, January 2006
- Gan, Zhehong
- Chem. Commun., Issue 45
Large-Scale Selective Functionalization of Alkanes
journal, March 2017
- Goldberg, Karen I.; Goldman, Alan S.
- Accounts of Chemical Research, Vol. 50, Issue 3
Intermolecular C–H Bond Activation of Alkanes and Arenes by NCN Pincer Iridium(III) Acetate Complexes Containing Bis(oxazolinyl)phenyl Ligands
journal, May 2012
- Ito, Jun-ichi; Kaneda, Tomoko; Nishiyama, Hisao
- Organometallics, Vol. 31, Issue 12
Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts
journal, March 2016
- Pelletier, Jérémie D. A.; Basset, Jean-Marie
- Accounts of Chemical Research, Vol. 49, Issue 4
Atomic-level organization of vicinal acid–base pairs through the chemisorption of aniline and derivatives onto mesoporous SBA15
journal, January 2016
- Hamzaoui, Bilel; Bendjeriou-Sedjerari, Anissa; Pump, Eva
- Chemical Science, Vol. 7, Issue 9
Use of DFT to achieve a rational understanding of acid?basic properties of ?-alumina surfaces
journal, August 2004
- Digne, M.
- Journal of Catalysis, Vol. 226, Issue 1
γ-Alumina: The Essential and Unexpected Role of Water for the Structure, Stability, and Reactivity of “Defect” Sites
journal, August 2012
- Wischert, Raphael; Laurent, Pierre; Copéret, Christophe
- Journal of the American Chemical Society, Vol. 134, Issue 35
Theoretical Study of the Dehydration Process of Boehmite to γ-Alumina
journal, June 2001
- Krokidis, Xénophon; Raybaud, Pascal; Gobichon, Anne-Elisabeth
- The Journal of Physical Chemistry B, Vol. 105, Issue 22
Homogeneous and Heterogeneous Catalysis: Bridging the Gap through Surface Organometallic Chemistry
journal, January 2003
- Copéret, Christophe; Chabanas, Mathieu; Petroff Saint-Arroman, Romain
- Angewandte Chemie International Edition, Vol. 42, Issue 2, p. 156-181
Activation of Low-Valent, Multiply M–M Bonded Group VI Dimers toward Catalytic Olefin Metathesis via Surface Organometallic Chemistry
journal, February 2020
- Chapovetsky, Alon; Langeslay, Ryan R.; Celik, Gokhan
- Organometallics, Vol. 39, Issue 7
Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica
journal, February 2018
- Camacho-Bunquin, Jeffrey; Ferrandon, Magali; Sohn, Hyuntae
- Journal of the American Chemical Society, Vol. 140, Issue 11
Bridging the Gap between Industrial and Well-Defined Supported Catalysts
journal, March 2018
- Copéret, Christophe; Allouche, Florian; Chan, Ka Wing
- Angewandte Chemie International Edition, Vol. 57, Issue 22
Understanding surface site structures and properties by first principles calculations: an experimental point of view!
journal, January 2017
- Comas-Vives, Aleix; Larmier, Kim; Copéret, Christophe
- Chemical Communications, Vol. 53, Issue 31
Dynamic nuclear polarization at high magnetic fields
journal, February 2008
- Maly, Thorsten; Debelouchina, Galia T.; Bajaj, Vikram S.
- The Journal of Chemical Physics, Vol. 128, Issue 5
Large Molecular Weight Nitroxide Biradicals Providing Efficient Dynamic Nuclear Polarization at Temperatures up to 200 K
journal, August 2013
- Zagdoun, Alexandre; Casano, Gilles; Ouari, Olivier
- Journal of the American Chemical Society, Vol. 135, Issue 34
Surface Termination of CsPbBr 3 Perovskite Quantum Dots Determined by Solid-State NMR Spectroscopy
journal, March 2020
- Chen, Yunhua; Smock, Sara R.; Flintgruber, Anne H.
- Journal of the American Chemical Society, Vol. 142, Issue 13
Surface Enhanced NMR Spectroscopy by Dynamic Nuclear Polarization
journal, November 2010
- Lesage, Anne; Lelli, Moreno; Gajan, David
- Journal of the American Chemical Society, Vol. 132, Issue 44
Dehydrogenation of Alkanes and Aliphatic Groups by Pincer-Ligated Metal Complexes
journal, September 2017
- Kumar, Akshai; Bhatti, Tariq M.; Goldman, Alan S.
- Chemical Reviews, Vol. 117, Issue 19
Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy
journal, March 2013
- Rossini, Aaron J.; Zagdoun, Alexandre; Lelli, Moreno
- Accounts of Chemical Research, Vol. 46, Issue 9
Silica-surface reorganization during organotin grafting evidenced by 119 Sn DNP SENS: a tandem reaction of gem-silanols and strained siloxane bridges
journal, January 2014
- Conley, Matthew P.; Rossini, Aaron J.; Comas-Vives, Aleix
- Phys. Chem. Chem. Phys., Vol. 16, Issue 33
Rotational-echo double-resonance NMR
journal, January 1989
- Gullion, Terry; Schaefer, Jacob
- Journal of Magnetic Resonance (1969), Vol. 81, Issue 1
A two-dimensional nuclear Overhauser enhancement (2D NOE) experiment for the elucidation of complete proton-proton cross-relaxation networks in biological macromolecules
journal, July 1980
- Kumar, Anil; Ernst, R. R.; Wüthrich, K.
- Biochemical and Biophysical Research Communications, Vol. 95, Issue 1
β-Hydride Elimination and C–H Activation by an Iridium Acetate Complex, Catalyzed by Lewis Acids. Alkane Dehydrogenation Cocatalyzed by Lewis Acids and [2,6-Bis(4,4-dimethyloxazolinyl)-3,5-dimethylphenyl]iridium
journal, May 2017
- Gao, Yang; Guan, Changjian; Zhou, Meng
- Journal of the American Chemical Society, Vol. 139, Issue 18
High-resolution 1H NMR in solids with frequency-switched multiple-pulse sequences
journal, September 1993
- Levitt, M. H.; Kolbert, A. C.; Bielecki, A.
- Solid State Nuclear Magnetic Resonance, Vol. 2, Issue 4
The Structure of Molecular and Surface Platinum Sites Determined by DNP-SENS and Fast MAS 195 Pt Solid-State NMR Spectroscopy
journal, October 2020
- Venkatesh, Amrit; Lund, Alicia; Rochlitz, Lukas
- Journal of the American Chemical Society, Vol. 142, Issue 44
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008
- Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
- Physical Review Letters, Vol. 100, Issue 13
Surface Organometallic and Coordination Chemistry toward Single-Site Heterogeneous Catalysts: Strategies, Methods, Structures, and Activities
journal, January 2016
- Copéret, Christophe; Comas-Vives, Aleix; Conley, Matthew P.
- Chemical Reviews, Vol. 116, Issue 2
Improved strategies for DNP-enhanced 2D 1H-X heteronuclear correlation spectroscopy of surfaces
journal, October 2017
- Kobayashi, Takeshi; Perras, Frédéric A.; Chaudhary, Umesh
- Solid State Nuclear Magnetic Resonance, Vol. 87
Single-Site Heterogeneous Catalysts: From Synthesis to NMR Signal Enhancement
journal, November 2018
- Burueva, Dudari B.; Kovtunova, Larisa M.; Bukhtiyarov, Valerii I.
- Chemistry - A European Journal, Vol. 25, Issue 6
Three-Dimensional Structure Determination of Surface Sites
journal, January 2017
- Berruyer, Pierrick; Lelli, Moreno; Conley, Matthew P.
- Journal of the American Chemical Society, Vol. 139, Issue 2
Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990
- Vanderbilt, David
- Physical Review B, Vol. 41, Issue 11, p. 7892-7895
Validation of Protein Structure from Anisotropic Carbonyl Chemical Shifts in a Dilute Liquid Crystalline Phase
journal, July 1998
- Cornilescu, Gabriel; Marquardt, John L.; Ottiger, Marcel
- Journal of the American Chemical Society, Vol. 120, Issue 27
Multiple-scattering calculations of x-ray-absorption spectra
journal, July 1995
- Zabinsky, S. I.; Rehr, J. J.; Ankudinov, A.
- Physical Review B, Vol. 52, Issue 4
Evidence for Metal–Surface Interactions and Their Role in Stabilizing Well-Defined Immobilized Ru–NHC Alkene Metathesis Catalysts
journal, February 2013
- Samantaray, Manoja K.; Alauzun, Johan; Gajan, David
- Journal of the American Chemical Society, Vol. 135, Issue 8
First principles methods using CASTEP
journal, January 2005
- Clark, Stewart J.; Segall, Matthew D.; Pickard, Chris J.
- Zeitschrift für Kristallographie - Crystalline Materials, Vol. 220, Issue 5/6
Active Sites in Supported Single-Site Catalysts: An NMR Perspective
journal, July 2017
- Copéret, Christophe; Liao, Wei-Chih; Gordon, Christopher P.
- Journal of the American Chemical Society, Vol. 139, Issue 31
Atomistic Description of Reaction Intermediates for Supported Metathesis Catalysts Enabled by DNP SENS
journal, March 2016
- Ong, Ta-Chung; Liao, Wei-Chih; Mougel, Victor
- Angewandte Chemie International Edition, Vol. 55, Issue 15
Dynamic Nuclear Polarization Solid-State NMR in Heterogeneous Catalysis Research
journal, October 2015
- Kobayashi, Takeshi; Perras, Frédéric A.; Slowing, Igor I.
- ACS Catalysis, Vol. 5, Issue 12
The Comparison between Single Atom Catalysis and Surface Organometallic Catalysis
journal, October 2019
- Samantaray, Manoja K.; D’Elia, Valerio; Pump, Eva
- Chemical Reviews, Vol. 120, Issue 2
A Well-Defined Pd Hybrid Material for the Z -Selective Semihydrogenation of Alkynes Characterized at the Molecular Level by DNP SENS
journal, August 2013
- Conley, Matthew P.; Drost, Ruben M.; Baffert, Mathieu
- Chemistry - A European Journal, Vol. 19, Issue 37
Electrophilic Organoiridium(III) Pincer Complexes on Sulfated Zirconia for Hydrocarbon Activation and Functionalization
journal, March 2019
- Syed, Zoha H.; Kaphan, David M.; Perras, Frédéric A.
- Journal of the American Chemical Society, Vol. 141, Issue 15