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

Abstract

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. Strongly acidic modified metal oxides such as sulfated zirconia engender high levels of activity toward electrophilic bond activation of both sp(2) 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 Bronsted acidity.

Authors:
 [1]; ORCiD logo [1];  [2]; ORCiD logo [3];  [1];  [1]; ORCiD logo [1]
  1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
  2. U.S. DOE Ames Laboratory, Ames, Iowa 50011, United States
  3. U.S. DOE Ames Laboratory, Ames, Iowa 50011, United States; Department of Chemistry, Iowa State University, Ames, Iowa 50011, 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:
1461450
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 6; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

Citation Formats

Kaphan, David M., Klet, Rachel C., Perras, Frédéric 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., 2018. Web. doi:10.1021/acscatal.8b00855.
Kaphan, David M., Klet, Rachel C., Perras, Frédéric 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, Frédéric A., Pruski, Marek, Yang, Ce, Kropf, A. Jeremy, and Delferro, Massimiliano. Tue . "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_1461450,
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, Frédéric 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. Strongly acidic modified metal oxides such as sulfated zirconia engender high levels of activity toward electrophilic bond activation of both sp(2) 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 Bronsted acidity.},
doi = {10.1021/acscatal.8b00855},
journal = {ACS Catalysis},
issn = {2155-5435},
number = 6,
volume = 8,
place = {United States},
year = {2018},
month = {5}
}