Evidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides
Abstract
The chemical and electronic interaction of organometallic species with metal oxide support materials is of fundamental importance for the development of new classes of catalytic materials. Chemisorption of Cp*(PMe3)IrMe2 on sulfated alu-mina (SA) and sulfated zirconia (SZ) led to an unexpected redox mechanism for deuteration of the ancillary Cp* ligand. Evidence for this oxidative mechanism was provided by studying the analogous homogeneous reactivity of the organome-tallic precursors toward trityl cation ([Ph3C]+), a Lewis acid known to effect formal hydride abstraction by one electron oxidation followed by hydrogen abstraction. Organometallic deuterium incorporation was found to be correlated with surface sulfate concentration, as well as the extent of dehydration under thermal activation conditions of sulfated alumi-na and sulfated zirconia supports. Surface sulfate concentration dependence, in conjunction with a computational study of surface electron affinity, indicates an electron deficient pyrosulfate species as the redox active moiety. These results provide further evidence for the ability of sulfated metal oxides to participate in redox chemistry not only toward organ-ometallic complexes, but also in the larger context of their application as catalysts for the transformation of light alkanes.
- Authors:
-
[1];
[1];
[3];
[4];
[1]
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Ames Lab., Ames, IA (United States)
- Ames Lab. and Iowa State Univ., Ames, IA (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States); Illinois Institute of Technology, Chicago, IL (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)
- OSTI Identifier:
- 1435752
- Alternate Identifier(s):
- OSTI ID: 1460729
- Report Number(s):
- IS-J-9600
Journal ID: ISSN 0002-7863
- Grant/Contract Number:
- AC02-06CH11357; AC02-07CH11358
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 140; Journal Issue: 20; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Klet, Rachel C., Kaphan, David M., Liu, Cong, Yang, Ce, Kropf, A. Jeremy, Perras, Frederic A., Pruski, Marek, Hock, Adam S., and Delferro, Massimiliano. Evidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides. United States: N. p., 2018.
Web. doi:10.1021/jacs.8b00995.
Klet, Rachel C., Kaphan, David M., Liu, Cong, Yang, Ce, Kropf, A. Jeremy, Perras, Frederic A., Pruski, Marek, Hock, Adam S., & Delferro, Massimiliano. Evidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides. United States. https://doi.org/10.1021/jacs.8b00995
Klet, Rachel C., Kaphan, David M., Liu, Cong, Yang, Ce, Kropf, A. Jeremy, Perras, Frederic A., Pruski, Marek, Hock, Adam S., and Delferro, Massimiliano. Mon .
"Evidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides". United States. https://doi.org/10.1021/jacs.8b00995. https://www.osti.gov/servlets/purl/1435752.
@article{osti_1435752,
title = {Evidence for Redox Mechanisms in Organometallic Chemisorption and Reactivity on Sulfated Metal Oxides},
author = {Klet, Rachel C. and Kaphan, David M. and Liu, Cong and Yang, Ce and Kropf, A. Jeremy and Perras, Frederic A. and Pruski, Marek and Hock, Adam S. and Delferro, Massimiliano},
abstractNote = {The chemical and electronic interaction of organometallic species with metal oxide support materials is of fundamental importance for the development of new classes of catalytic materials. Chemisorption of Cp*(PMe3)IrMe2 on sulfated alu-mina (SA) and sulfated zirconia (SZ) led to an unexpected redox mechanism for deuteration of the ancillary Cp* ligand. Evidence for this oxidative mechanism was provided by studying the analogous homogeneous reactivity of the organome-tallic precursors toward trityl cation ([Ph3C]+), a Lewis acid known to effect formal hydride abstraction by one electron oxidation followed by hydrogen abstraction. Organometallic deuterium incorporation was found to be correlated with surface sulfate concentration, as well as the extent of dehydration under thermal activation conditions of sulfated alumi-na and sulfated zirconia supports. Surface sulfate concentration dependence, in conjunction with a computational study of surface electron affinity, indicates an electron deficient pyrosulfate species as the redox active moiety. These results provide further evidence for the ability of sulfated metal oxides to participate in redox chemistry not only toward organ-ometallic complexes, but also in the larger context of their application as catalysts for the transformation of light alkanes.},
doi = {10.1021/jacs.8b00995},
journal = {Journal of the American Chemical Society},
number = 20,
volume = 140,
place = {United States},
year = {Mon Apr 09 00:00:00 EDT 2018},
month = {Mon Apr 09 00:00:00 EDT 2018}
}
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