skip to main content

DOE PAGESDOE PAGES

This content will become publicly available on May 11, 2019

Title: Surface Organometallic Chemistry of Supported Iridium(III) as a Probe for Organotransition Metal–Support Interactions in C–H Activation

Systematic study of the interactions between organometallic catalysts and metal oxide support materials is essential for the realization of rational design in heterogeneous catalysis. Herein we describe the stoichiometric and catalytic chemistry of a [Cp*(PMe 3)Ir(III)] complex chemisorbed on a variety of acidic metal oxides as a multifaceted probe for stereoelectronic communication between the support and organometallic center. Electrophilic bond activation was explored in the context of stoichiometric hydrogenolysis as well as catalytic H/D exchange. Further information was obtained from the observation of processes related to dynamic exchange between grafted organometallic species and those in solution. The supported organometallic species were characterized by a variety of spectroscopic techniques including dynamic nuclear polarization-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy. Finally, strongly acidic modified metal oxides such as sulfated zirconia engender high levels of activity toward electrophilic bond activation of both sp 2 and sp 3 C–H bonds, including the rapid deuteration of methane at room temperature; however, the global trend for the supports studied here does not suggest a direct correlation between activity and surface Brønsted acidity.
Authors:
 [1] ; ORCiD logo [1] ;  [2] ; ORCiD logo [3] ;  [1] ;  [1] ; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Ames Lab., Ames, IA (United States)
  3. Ames Lab. and Iowa State Univ., Ames, IA (United States). Dept. of Chemistry
Publication Date:
Report Number(s):
IS-J-9599
Journal ID: ISSN 2155-5435
Grant/Contract Number:
AC02-07CH11358; AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 6; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Research Org:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; C−H activation; heterogeneous catalysis; solid-state NMR; sulfated oxides; surface organometallic catalysis
OSTI Identifier:
1440975

Kaphan, David M., Klet, Rachel C., Perras, Frederic A., Pruski, Marek, Yang, Ce, Kropf, A. Jeremy, and Delferro, Massimiliano. Surface Organometallic Chemistry of Supported Iridium(III) as a Probe for Organotransition Metal–Support Interactions in C–H Activation. United States: N. p., Web. doi:10.1021/acscatal.8b00855.
Kaphan, David M., Klet, Rachel C., Perras, Frederic A., Pruski, Marek, Yang, Ce, Kropf, A. Jeremy, & Delferro, Massimiliano. Surface Organometallic Chemistry of Supported Iridium(III) as a Probe for Organotransition Metal–Support Interactions in C–H Activation. United States. doi:10.1021/acscatal.8b00855.
Kaphan, David M., Klet, Rachel C., Perras, Frederic A., Pruski, Marek, Yang, Ce, Kropf, A. Jeremy, and Delferro, Massimiliano. 2018. "Surface Organometallic Chemistry of Supported Iridium(III) as a Probe for Organotransition Metal–Support Interactions in C–H Activation". United States. doi:10.1021/acscatal.8b00855.
@article{osti_1440975,
title = {Surface Organometallic Chemistry of Supported Iridium(III) as a Probe for Organotransition Metal–Support Interactions in C–H Activation},
author = {Kaphan, David M. and Klet, Rachel C. and Perras, Frederic A. and Pruski, Marek and Yang, Ce and Kropf, A. Jeremy and Delferro, Massimiliano},
abstractNote = {Systematic study of the interactions between organometallic catalysts and metal oxide support materials is essential for the realization of rational design in heterogeneous catalysis. Herein we describe the stoichiometric and catalytic chemistry of a [Cp*(PMe3)Ir(III)] complex chemisorbed on a variety of acidic metal oxides as a multifaceted probe for stereoelectronic communication between the support and organometallic center. Electrophilic bond activation was explored in the context of stoichiometric hydrogenolysis as well as catalytic H/D exchange. Further information was obtained from the observation of processes related to dynamic exchange between grafted organometallic species and those in solution. The supported organometallic species were characterized by a variety of spectroscopic techniques including dynamic nuclear polarization-enhanced solid-state NMR spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, and X-ray absorption spectroscopy. Finally, strongly acidic modified metal oxides such as sulfated zirconia engender high levels of activity toward electrophilic bond activation of both sp2 and sp3 C–H bonds, including the rapid deuteration of methane at room temperature; however, the global trend for the supports studied here does not suggest a direct correlation between activity and surface Brønsted acidity.},
doi = {10.1021/acscatal.8b00855},
journal = {ACS Catalysis},
number = 6,
volume = 8,
place = {United States},
year = {2018},
month = {5}
}