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Title: 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:
ORCiD logo [1];  [1]; ORCiD logo [2];  [3]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [4]
  1. Ames Lab., Ames, IA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. 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}
}

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