Hydrogenation of N-Heteroarenes Using Rhodium Precatalysts: Reductive Elimination Leads to Formation of Multimetallic Clusters
Abstract
A rhodium-catalyzed method for the hydrogenation of N-heteroarenes is described here. A diverse array of unsubstituted N-heteroarenes including pyridine, pyrrole and pyrazine, traditionally challenging substrates for hydrogenation, were successfully hydrogenated using the organometallic precatalysts, (η5-C5Me5)Rh(N-C)H (N-C = 2-phenylpyridinyl (ppy) or benzo[h]quinolinyl (bq)). In addition, the hydrogenation of polyaromatic N-heteroarenes exhibited uncommon chemoselectivity. Studies into catalyst activation revealed that photochemical or thermal activation of (η5-C5Me5)Rh(bq)H induced C(sp2)–H reductive elimination and generated the bimetallic complex, [(η5-C5Me5)Rh(µ2,η2-bq)Rh(η5-C5Me5)H]. In the presence of H2 both of the (η5-C5Me5)Rh(N-C)H precursors and [(η5-C5Me5)Rh(µ2,η2-bq)Rh(η5-C5Me5)H] converted to a pentametallic rhodium hydride cluster, (η5-C5Me5)4Rh5H7, the structure of which was established by NMR spectroscopy, X-ray and neutron diffraction. Kinetic studies on pyridine hydrogenation were conducted with each of the isolated rhodium complexes to identify catalytically relevant species. The data are most consistent with hydrogenation catalysis prompted by an unobserved multimetallic cluster with formation of (η5-C5Me5)4Rh5H7 serving as a deactivation pathway.
- Authors:
-
[1];
[1];
[1];
[2];
[1]
- Princeton Univ., NJ (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Princeton Univ., NJ (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; Samsung; German Research Foundation (DFG); Natural Sciences and Engineering Research Council of Canada (NSERC); National Science Foundation (NSF)
- OSTI Identifier:
- 1569484
- Grant/Contract Number:
- SC0006498; AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 141; Journal Issue: 44; 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
Kim, Sangmin, Loose, Florian, Bezdek, Máté J., Wang, Xiaoping, and Chirik, Paul J. Hydrogenation of N-Heteroarenes Using Rhodium Precatalysts: Reductive Elimination Leads to Formation of Multimetallic Clusters. United States: N. p., 2019.
Web. doi:10.1021/jacs.9b09540.
Kim, Sangmin, Loose, Florian, Bezdek, Máté J., Wang, Xiaoping, & Chirik, Paul J. Hydrogenation of N-Heteroarenes Using Rhodium Precatalysts: Reductive Elimination Leads to Formation of Multimetallic Clusters. United States. https://doi.org/10.1021/jacs.9b09540
Kim, Sangmin, Loose, Florian, Bezdek, Máté J., Wang, Xiaoping, and Chirik, Paul J. Mon .
"Hydrogenation of N-Heteroarenes Using Rhodium Precatalysts: Reductive Elimination Leads to Formation of Multimetallic Clusters". United States. https://doi.org/10.1021/jacs.9b09540. https://www.osti.gov/servlets/purl/1569484.
@article{osti_1569484,
title = {Hydrogenation of N-Heteroarenes Using Rhodium Precatalysts: Reductive Elimination Leads to Formation of Multimetallic Clusters},
author = {Kim, Sangmin and Loose, Florian and Bezdek, Máté J. and Wang, Xiaoping and Chirik, Paul J.},
abstractNote = {A rhodium-catalyzed method for the hydrogenation of N-heteroarenes is described here. A diverse array of unsubstituted N-heteroarenes including pyridine, pyrrole and pyrazine, traditionally challenging substrates for hydrogenation, were successfully hydrogenated using the organometallic precatalysts, (η5-C5Me5)Rh(N-C)H (N-C = 2-phenylpyridinyl (ppy) or benzo[h]quinolinyl (bq)). In addition, the hydrogenation of polyaromatic N-heteroarenes exhibited uncommon chemoselectivity. Studies into catalyst activation revealed that photochemical or thermal activation of (η5-C5Me5)Rh(bq)H induced C(sp2)–H reductive elimination and generated the bimetallic complex, [(η5-C5Me5)Rh(µ2,η2-bq)Rh(η5-C5Me5)H]. In the presence of H2 both of the (η5-C5Me5)Rh(N-C)H precursors and [(η5-C5Me5)Rh(µ2,η2-bq)Rh(η5-C5Me5)H] converted to a pentametallic rhodium hydride cluster, (η5-C5Me5)4Rh5H7, the structure of which was established by NMR spectroscopy, X-ray and neutron diffraction. Kinetic studies on pyridine hydrogenation were conducted with each of the isolated rhodium complexes to identify catalytically relevant species. The data are most consistent with hydrogenation catalysis prompted by an unobserved multimetallic cluster with formation of (η5-C5Me5)4Rh5H7 serving as a deactivation pathway.},
doi = {10.1021/jacs.9b09540},
journal = {Journal of the American Chemical Society},
number = 44,
volume = 141,
place = {United States},
year = {Mon Oct 07 00:00:00 EDT 2019},
month = {Mon Oct 07 00:00:00 EDT 2019}
}
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