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Title: Dendrimer-Stabilized Metal Nanoparticles as Efficient Catalysts for Reversible Dehydrogenation/Hydrogenation of N-Heterocycles

Abstract

Nanoparticles (Pd, Pt, Rh) stabilized by G4OH PAMAM dendrimers and supported in SBA-15 (MNPs/SBA-15 with M = Pd, Pt, Rh) were efficiently used as catalysts in the acceptorless dehydrogenation of tetrahydroquinoline/indoline derivatives in toluene (release of H 2) at 130 °C. These catalysts are air stable, very active, robust, and recyclable during the process. The reverse hydrogenation reaction of quinoline derivatives (H 2 storage) was also optimized and successfully performed in the presence of the same catalysts in toluene at 60 °C under only 1 atm of hydrogen gas. Such catalysts may be essential for the adoption of organic hydrogen-storage materials as an alternative to petroleum-derived fuels. Hot filtration test confirmed that the reaction follows a heterogeneous pathway. Moreover, PdNPs/SBA-15 was an excellent catalyst for the direct arylation at the C-2 position (via C–H activation) of indole in water in the presense of a hypervalent iodine oxidant. Thus, a one-pot dehydrogenation/direct arylation cascade reaction between indoline and an arylated agent was efficaciously performed in water, demonstrating the potential of the system to catalyze tandem heterogeneous/homogeneous processes by choice of the appropriate oxidant/reductant.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Science Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1411097
Alternate Identifier(s):
OSTI ID: 1464157
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 49; 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

Deraedt, Christophe, Ye, Rong, Ralston, Walter T., Toste, F. Dean, and Somorjai, Gabor A.. Dendrimer-Stabilized Metal Nanoparticles as Efficient Catalysts for Reversible Dehydrogenation/Hydrogenation of N-Heterocycles. United States: N. p., 2017. Web. doi:10.1021/jacs.7b10768.
Deraedt, Christophe, Ye, Rong, Ralston, Walter T., Toste, F. Dean, & Somorjai, Gabor A.. Dendrimer-Stabilized Metal Nanoparticles as Efficient Catalysts for Reversible Dehydrogenation/Hydrogenation of N-Heterocycles. United States. doi:10.1021/jacs.7b10768.
Deraedt, Christophe, Ye, Rong, Ralston, Walter T., Toste, F. Dean, and Somorjai, Gabor A.. Thu . "Dendrimer-Stabilized Metal Nanoparticles as Efficient Catalysts for Reversible Dehydrogenation/Hydrogenation of N-Heterocycles". United States. doi:10.1021/jacs.7b10768.
@article{osti_1411097,
title = {Dendrimer-Stabilized Metal Nanoparticles as Efficient Catalysts for Reversible Dehydrogenation/Hydrogenation of N-Heterocycles},
author = {Deraedt, Christophe and Ye, Rong and Ralston, Walter T. and Toste, F. Dean and Somorjai, Gabor A.},
abstractNote = {Nanoparticles (Pd, Pt, Rh) stabilized by G4OH PAMAM dendrimers and supported in SBA-15 (MNPs/SBA-15 with M = Pd, Pt, Rh) were efficiently used as catalysts in the acceptorless dehydrogenation of tetrahydroquinoline/indoline derivatives in toluene (release of H2) at 130 °C. These catalysts are air stable, very active, robust, and recyclable during the process. The reverse hydrogenation reaction of quinoline derivatives (H2 storage) was also optimized and successfully performed in the presence of the same catalysts in toluene at 60 °C under only 1 atm of hydrogen gas. Such catalysts may be essential for the adoption of organic hydrogen-storage materials as an alternative to petroleum-derived fuels. Hot filtration test confirmed that the reaction follows a heterogeneous pathway. Moreover, PdNPs/SBA-15 was an excellent catalyst for the direct arylation at the C-2 position (via C–H activation) of indole in water in the presense of a hypervalent iodine oxidant. Thus, a one-pot dehydrogenation/direct arylation cascade reaction between indoline and an arylated agent was efficaciously performed in water, demonstrating the potential of the system to catalyze tandem heterogeneous/homogeneous processes by choice of the appropriate oxidant/reductant.},
doi = {10.1021/jacs.7b10768},
journal = {Journal of the American Chemical Society},
number = 49,
volume = 139,
place = {United States},
year = {Thu Nov 16 00:00:00 EST 2017},
month = {Thu Nov 16 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/jacs.7b10768

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Cited by: 4 works
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