Revealing the Configuration and Conformation of Surface Organometallic Catalysts with DNP-Enhanced NMR

Perras, Frédéric A.; Paterson, Alexander L.; Syed, Zoha H.; Kropf, A. Jeremy; Kaphan, David M.; Delferro, Massimiliano; Pruski, Marek

doi:10.1021/acs.jpcc.1c03176

Title: Revealing the Configuration and Conformation of Surface Organometallic Catalysts with DNP-Enhanced NMR

Journal Article · Fri Jun 11 00:00:00 EDT 2021 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/acs.jpcc.1c03176· OSTI ID:1798866

^[1]; Paterson, Alexander L. ^[1];

^[2]; Kropf, A. Jeremy ^[3];

^[3];

^[4]

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)

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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Ames Lab., Ames, IA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

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

Grant/Contract Number:: AC-02-07CH11358; DGE-1842165; AC-02-06CH11357

OSTI ID:: 1798866

Alternate ID(s):: OSTI ID: 1831741

Report Number(s):: IS-J-10,522

Journal Information:: Journal of Physical Chemistry. C, Vol. 125, Issue 24; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (52)

Structural models of activated γ-alumina surfaces revisited: Thermodynamics, NMR and IR spectroscopies from ab initio calculations Ferreira, Ary R.; Küçükbenli, Emine; de Gironcoli, Stefano Chemical Physics, Vol. 423 https://doi.org/10.1016/j.chemphys.2013.06.024	journal	September 2013
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Molecular design of heterogeneous catalysts: the case of olefin metathesis Copéret, Christophe New J. Chem., Vol. 28, Issue 1 https://doi.org/10.1039/B310662B	journal	January 2004
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Observing the three-dimensional dynamics of supported metal complexes Paterson, Alexander L.; Liu, Da-Jiang; Kanbur, Uddhav Inorganic Chemistry Frontiers, Vol. 8, Issue 6 https://doi.org/10.1039/D0QI01241F	journal	January 2021
Catalysis and Surface Organometallic Chemistry: A View from Theory and Simulations Sautet, Philippe; Delbecq, Françoise Chemical Reviews, Vol. 110, Issue 3 https://doi.org/10.1021/cr900295b	journal	March 2010
Local Structures and Heterogeneity of Silica-Supported M(III) Sites Evidenced by EPR, IR, NMR, and Luminescence Spectroscopies Delley, Murielle F.; Lapadula, Giuseppe; Núñez-Zarur, Francisco Journal of the American Chemical Society, Vol. 139, Issue 26 https://doi.org/10.1021/jacs.7b02179	journal	June 2017
Relaxation of Crystals with the Quasi-Newton Method Pfrommer, Bernd G.; Côté, Michel; Louie, Steven G. Journal of Computational Physics, Vol. 131, Issue 1 https://doi.org/10.1006/jcph.1996.5612	journal	February 1997
Measurement of Aluminum-Carbon Distances Using S-RESPDOR NMR Experiments Pourpoint, Frédérique; Trébosc, Julien; Gauvin, Régis M. ChemPhysChem, Vol. 13, Issue 16 https://doi.org/10.1002/cphc.201200490	journal	September 2012
Characterizing Substrate–Surface Interactions on Alumina-Supported Metal Catalysts by Dynamic Nuclear Polarization-Enhanced Double-Resonance NMR Spectroscopy Perras, Frédéric A.; Padmos, J. Daniel; Johnson, Robert L. Journal of the American Chemical Society, Vol. 139, Issue 7 https://doi.org/10.1021/jacs.6b11408	journal	February 2017
Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data Tkatchenko, Alexandre; Scheffler, Matthias Physical Review Letters, Vol. 102, Issue 7 https://doi.org/10.1103/PhysRevLett.102.073005	journal	February 2009
Measuring multiple carbon–nitrogen distances in natural abundant solids using R-RESPDOR NMR Gan, Zhehong Chem. Commun., Issue 45 https://doi.org/10.1039/B611447D	journal	January 2006
Large-Scale Selective Functionalization of Alkanes Goldberg, Karen I.; Goldman, Alan S. Accounts of Chemical Research, Vol. 50, Issue 3 https://doi.org/10.1021/acs.accounts.6b00621	journal	March 2017
Intermolecular C–H Bond Activation of Alkanes and Arenes by NCN Pincer Iridium(III) Acetate Complexes Containing Bis(oxazolinyl)phenyl Ligands Ito, Jun-ichi; Kaneda, Tomoko; Nishiyama, Hisao Organometallics, Vol. 31, Issue 12 https://doi.org/10.1021/om3002137	journal	May 2012
Catalysis by Design: Well-Defined Single-Site Heterogeneous Catalysts Pelletier, Jérémie D. A.; Basset, Jean-Marie Accounts of Chemical Research, Vol. 49, Issue 4 https://doi.org/10.1021/acs.accounts.5b00518	journal	March 2016
Atomic-level organization of vicinal acid–base pairs through the chemisorption of aniline and derivatives onto mesoporous SBA15 Hamzaoui, Bilel; Bendjeriou-Sedjerari, Anissa; Pump, Eva Chemical Science, Vol. 7, Issue 9 https://doi.org/10.1039/C6SC01229A	journal	January 2016
Use of DFT to achieve a rational understanding of acid?basic properties of ?-alumina surfaces Digne, M. Journal of Catalysis, Vol. 226, Issue 1 https://doi.org/10.1016/j.jcat.2004.04.020	journal	August 2004
γ-Alumina: The Essential and Unexpected Role of Water for the Structure, Stability, and Reactivity of “Defect” Sites Wischert, Raphael; Laurent, Pierre; Copéret, Christophe Journal of the American Chemical Society, Vol. 134, Issue 35 https://doi.org/10.1021/ja3042383	journal	August 2012
Theoretical Study of the Dehydration Process of Boehmite to γ-Alumina Krokidis, Xénophon; Raybaud, Pascal; Gobichon, Anne-Elisabeth The Journal of Physical Chemistry B, Vol. 105, Issue 22 https://doi.org/10.1021/jp0038310	journal	June 2001
Homogeneous and Heterogeneous Catalysis: Bridging the Gap through Surface Organometallic Chemistry Copéret, Christophe; Chabanas, Mathieu; Petroff Saint-Arroman, Romain Angewandte Chemie International Edition, Vol. 42, Issue 2, p. 156-181 https://doi.org/10.1002/anie.200390072	journal	January 2003
Activation of Low-Valent, Multiply M–M Bonded Group VI Dimers toward Catalytic Olefin Metathesis via Surface Organometallic Chemistry Chapovetsky, Alon; Langeslay, Ryan R.; Celik, Gokhan Organometallics, Vol. 39, Issue 7 https://doi.org/10.1021/acs.organomet.9b00787	journal	February 2020
Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica Camacho-Bunquin, Jeffrey; Ferrandon, Magali; Sohn, Hyuntae Journal of the American Chemical Society, Vol. 140, Issue 11 https://doi.org/10.1021/jacs.7b11981	journal	February 2018
Bridging the Gap between Industrial and Well-Defined Supported Catalysts Copéret, Christophe; Allouche, Florian; Chan, Ka Wing Angewandte Chemie International Edition, Vol. 57, Issue 22 https://doi.org/10.1002/anie.201702387	journal	March 2018
Understanding surface site structures and properties by first principles calculations: an experimental point of view! Comas-Vives, Aleix; Larmier, Kim; Copéret, Christophe Chemical Communications, Vol. 53, Issue 31 https://doi.org/10.1039/C7CC01101F	journal	January 2017
Dynamic nuclear polarization at high magnetic fields Maly, Thorsten; Debelouchina, Galia T.; Bajaj, Vikram S. The Journal of Chemical Physics, Vol. 128, Issue 5 https://doi.org/10.1063/1.2833582	journal	February 2008
Large Molecular Weight Nitroxide Biradicals Providing Efficient Dynamic Nuclear Polarization at Temperatures up to 200 K Zagdoun, Alexandre; Casano, Gilles; Ouari, Olivier Journal of the American Chemical Society, Vol. 135, Issue 34 https://doi.org/10.1021/ja405813t	journal	August 2013
Surface Termination of CsPbBr ₃ Perovskite Quantum Dots Determined by Solid-State NMR Spectroscopy Chen, Yunhua; Smock, Sara R.; Flintgruber, Anne H. Journal of the American Chemical Society, Vol. 142, Issue 13 https://doi.org/10.1021/jacs.9b13396	journal	March 2020
Surface Enhanced NMR Spectroscopy by Dynamic Nuclear Polarization Lesage, Anne; Lelli, Moreno; Gajan, David Journal of the American Chemical Society, Vol. 132, Issue 44 https://doi.org/10.1021/ja104771z	journal	November 2010
Dehydrogenation of Alkanes and Aliphatic Groups by Pincer-Ligated Metal Complexes Kumar, Akshai; Bhatti, Tariq M.; Goldman, Alan S. Chemical Reviews, Vol. 117, Issue 19 https://doi.org/10.1021/acs.chemrev.7b00247	journal	September 2017
Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy Rossini, Aaron J.; Zagdoun, Alexandre; Lelli, Moreno Accounts of Chemical Research, Vol. 46, Issue 9 https://doi.org/10.1021/ar300322x	journal	March 2013
Silica-surface reorganization during organotin grafting evidenced by ¹¹⁹ Sn DNP SENS: a tandem reaction of gem-silanols and strained siloxane bridges Conley, Matthew P.; Rossini, Aaron J.; Comas-Vives, Aleix Phys. Chem. Chem. Phys., Vol. 16, Issue 33 https://doi.org/10.1039/C4CP01973C	journal	January 2014
Rotational-echo double-resonance NMR Gullion, Terry; Schaefer, Jacob Journal of Magnetic Resonance (1969), Vol. 81, Issue 1 https://doi.org/10.1016/0022-2364(89)90280-1	journal	January 1989
A two-dimensional nuclear Overhauser enhancement (2D NOE) experiment for the elucidation of complete proton-proton cross-relaxation networks in biological macromolecules Kumar, Anil; Ernst, R. R.; Wüthrich, K. Biochemical and Biophysical Research Communications, Vol. 95, Issue 1 https://doi.org/10.1016/0006-291X(80)90695-6	journal	July 1980
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 Gao, Yang; Guan, Changjian; Zhou, Meng Journal of the American Chemical Society, Vol. 139, Issue 18 https://doi.org/10.1021/jacs.6b12995	journal	May 2017
High-resolution 1H NMR in solids with frequency-switched multiple-pulse sequences Levitt, M. H.; Kolbert, A. C.; Bielecki, A. Solid State Nuclear Magnetic Resonance, Vol. 2, Issue 4 https://doi.org/10.1016/0926-2040(93)90021-E	journal	September 1993
The Structure of Molecular and Surface Platinum Sites Determined by DNP-SENS and Fast MAS ¹⁹⁵ Pt Solid-State NMR Spectroscopy Venkatesh, Amrit; Lund, Alicia; Rochlitz, Lukas Journal of the American Chemical Society, Vol. 142, Issue 44 https://doi.org/10.1021/jacs.0c09101	journal	October 2020
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 100, Issue 13 https://doi.org/10.1103/PhysRevLett.100.136406	journal	April 2008
Surface Organometallic and Coordination Chemistry toward Single-Site Heterogeneous Catalysts: Strategies, Methods, Structures, and Activities Copéret, Christophe; Comas-Vives, Aleix; Conley, Matthew P. Chemical Reviews, Vol. 116, Issue 2 https://doi.org/10.1021/acs.chemrev.5b00373	journal	January 2016
Improved strategies for DNP-enhanced 2D 1H-X heteronuclear correlation spectroscopy of surfaces Kobayashi, Takeshi; Perras, Frédéric A.; Chaudhary, Umesh Solid State Nuclear Magnetic Resonance, Vol. 87 https://doi.org/10.1016/j.ssnmr.2017.08.002	journal	October 2017
Single-Site Heterogeneous Catalysts: From Synthesis to NMR Signal Enhancement Burueva, Dudari B.; Kovtunova, Larisa M.; Bukhtiyarov, Valerii I. Chemistry - A European Journal, Vol. 25, Issue 6 https://doi.org/10.1002/chem.201803515	journal	November 2018
Three-Dimensional Structure Determination of Surface Sites Berruyer, Pierrick; Lelli, Moreno; Conley, Matthew P. Journal of the American Chemical Society, Vol. 139, Issue 2 https://doi.org/10.1021/jacs.6b10894	journal	January 2017
Soft self-consistent pseudopotentials in a generalized eigenvalue formalism Vanderbilt, David Physical Review B, Vol. 41, Issue 11, p. 7892-7895 https://doi.org/10.1103/PhysRevB.41.7892	journal	April 1990
Validation of Protein Structure from Anisotropic Carbonyl Chemical Shifts in a Dilute Liquid Crystalline Phase Cornilescu, Gabriel; Marquardt, John L.; Ottiger, Marcel Journal of the American Chemical Society, Vol. 120, Issue 27 https://doi.org/10.1021/ja9812610	journal	July 1998
Multiple-scattering calculations of x-ray-absorption spectra Zabinsky, S. I.; Rehr, J. J.; Ankudinov, A. Physical Review B, Vol. 52, Issue 4 https://doi.org/10.1103/PhysRevB.52.2995	journal	July 1995
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
First principles methods using CASTEP Clark, Stewart J.; Segall, Matthew D.; Pickard, Chris J. Zeitschrift für Kristallographie - Crystalline Materials, Vol. 220, Issue 5/6 https://doi.org/10.1524/zkri.220.5.567.65075	journal	January 2005
Active Sites in Supported Single-Site Catalysts: An NMR Perspective Copéret, Christophe; Liao, Wei-Chih; Gordon, Christopher P. Journal of the American Chemical Society, Vol. 139, Issue 31 https://doi.org/10.1021/jacs.6b12981	journal	July 2017
Atomistic Description of Reaction Intermediates for Supported Metathesis Catalysts Enabled by DNP SENS Ong, Ta-Chung; Liao, Wei-Chih; Mougel, Victor Angewandte Chemie International Edition, Vol. 55, Issue 15 https://doi.org/10.1002/anie.201510821	journal	March 2016
Dynamic Nuclear Polarization Solid-State NMR in Heterogeneous Catalysis Research Kobayashi, Takeshi; Perras, Frédéric A.; Slowing, Igor I. ACS Catalysis, Vol. 5, Issue 12 https://doi.org/10.1021/acscatal.5b02039	journal	October 2015
The Comparison between Single Atom Catalysis and Surface Organometallic Catalysis Samantaray, Manoja K.; D’Elia, Valerio; Pump, Eva Chemical Reviews, Vol. 120, Issue 2 https://doi.org/10.1021/acs.chemrev.9b00238	journal	October 2019
A Well-Defined Pd Hybrid Material for the Z -Selective Semihydrogenation of Alkynes Characterized at the Molecular Level by DNP SENS Conley, Matthew P.; Drost, Ruben M.; Baffert, Mathieu Chemistry - A European Journal, Vol. 19, Issue 37 https://doi.org/10.1002/chem.201302484	journal	August 2013
Electrophilic Organoiridium(III) Pincer Complexes on Sulfated Zirconia for Hydrocarbon Activation and Functionalization Syed, Zoha H.; Kaphan, David M.; Perras, Frédéric A. Journal of the American Chemical Society, Vol. 141, Issue 15 https://doi.org/10.1021/jacs.9b00896	journal	March 2019

Similar Records

Sulfated Zirconium Metal–Organic Frameworks as Well-Defined Supports for Enhancing Organometallic Catalysis

Journal Article · Sun Sep 11 00:00:00 EDT 2022 · Journal of the American Chemical Society · OSTI ID:1798866

Syed, Zoha H.; Mian, Mohammad Rasel; Patel, Roshan; +16 more

Electrophilic Organoiridium(III) Pincer Complexes on Sulfated Zirconia for Hydrocarbon Activation and Functionalization

Journal Article · Mon Apr 22 00:00:00 EDT 2019 · Journal of the American Chemical Society · OSTI ID:1798866

Syed, Zoha H.; Kaphan, David M.; Perras, Frédéric A.; +9 more

Activation of Low-Valent, Multiply M–M Bonded Group VI Dimers toward Catalytic Olefin Metathesis via Surface Organometallic Chemistry

Journal Article · Thu Feb 13 00:00:00 EST 2020 · Organometallics · OSTI ID:1798866

Chapovetsky, Alon; Langeslay, Ryan R.; Celik, Gokhan; +14 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chemical structure
oxides
organic compounds
transition metals
ligands

Title: Revealing the Configuration and Conformation of Surface Organometallic Catalysts with DNP-Enhanced NMR

Citation Formats

References (52)

Similar Records

Related Subjects