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Title: Nuclearity effects in supported, single-site Fe(ii) hydrogenation pre-catalysts

Abstract

Dimeric and monomeric supported single-site Fe(II) pre-catalysts on SiO 2 have been prepared via organometallic grafting and characterized with advanced spectroscopic techniques. Manipulation of the surface hydroxyl concentration on the support influences monomer/dimer formation. While both pre-catalysts are highly active in liquid-phase hydrogenation, the dimeric pre-catalyst is ~3× faster than the monomer. Here, preliminary XAS experiments on the H 2-activated samples suggest the active species are isolated Fe(II) sites.

Authors:
ORCiD logo [1];  [1];  [2];  [1];  [1];  [1];  [3];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1];  [1];  [1];  [2]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
  2. Argonne National Lab. (ANL), Lemont, IL (United States); Illinois Institute of Technology, Chicago, IL (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States); Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1477505
Alternate Identifier(s):
OSTI ID: 1460591
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 47; Journal Issue: 32; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Langeslay, Ryan R., Sohn, Hyuntae, Hu, Bo, Mohar, Jacob S., Ferrandon, Magali, Liu, Cong, Kim, Hacksung, Kropf, A. Jeremy, Yang, Ce, Niklas, Jens, Poluektov, Oleg G., Alp, E. Ercan, Ignacio-de Leon, Patricia, Sattelberger, Alfred P., Hock, Adam S., and Delferro, Massimiliano. Nuclearity effects in supported, single-site Fe(ii) hydrogenation pre-catalysts. United States: N. p., 2018. Web. doi:10.1039/c8dt02720j.
Langeslay, Ryan R., Sohn, Hyuntae, Hu, Bo, Mohar, Jacob S., Ferrandon, Magali, Liu, Cong, Kim, Hacksung, Kropf, A. Jeremy, Yang, Ce, Niklas, Jens, Poluektov, Oleg G., Alp, E. Ercan, Ignacio-de Leon, Patricia, Sattelberger, Alfred P., Hock, Adam S., & Delferro, Massimiliano. Nuclearity effects in supported, single-site Fe(ii) hydrogenation pre-catalysts. United States. doi:10.1039/c8dt02720j.
Langeslay, Ryan R., Sohn, Hyuntae, Hu, Bo, Mohar, Jacob S., Ferrandon, Magali, Liu, Cong, Kim, Hacksung, Kropf, A. Jeremy, Yang, Ce, Niklas, Jens, Poluektov, Oleg G., Alp, E. Ercan, Ignacio-de Leon, Patricia, Sattelberger, Alfred P., Hock, Adam S., and Delferro, Massimiliano. Tue . "Nuclearity effects in supported, single-site Fe(ii) hydrogenation pre-catalysts". United States. doi:10.1039/c8dt02720j. https://www.osti.gov/servlets/purl/1477505.
@article{osti_1477505,
title = {Nuclearity effects in supported, single-site Fe(ii) hydrogenation pre-catalysts},
author = {Langeslay, Ryan R. and Sohn, Hyuntae and Hu, Bo and Mohar, Jacob S. and Ferrandon, Magali and Liu, Cong and Kim, Hacksung and Kropf, A. Jeremy and Yang, Ce and Niklas, Jens and Poluektov, Oleg G. and Alp, E. Ercan and Ignacio-de Leon, Patricia and Sattelberger, Alfred P. and Hock, Adam S. and Delferro, Massimiliano},
abstractNote = {Dimeric and monomeric supported single-site Fe(II) pre-catalysts on SiO2 have been prepared via organometallic grafting and characterized with advanced spectroscopic techniques. Manipulation of the surface hydroxyl concentration on the support influences monomer/dimer formation. While both pre-catalysts are highly active in liquid-phase hydrogenation, the dimeric pre-catalyst is ~3× faster than the monomer. Here, preliminary XAS experiments on the H2-activated samples suggest the active species are isolated Fe(II) sites.},
doi = {10.1039/c8dt02720j},
journal = {Dalton Transactions},
number = 32,
volume = 47,
place = {United States},
year = {2018},
month = {7}
}

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Figures / Tables:

Figure 1 Figure 1: Raman spectra of 1 (red), SiO2-700 (teal), mesitylene (pink), [Fe(µ-Mes)Mes]2 (orange), 2 (blue) and SiO2-200 (black)

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.