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Dehydrogenation of ammonia-borane by cationic Pd(II) and Ni(II) complexes in a nitromethane medium: hydrogen release and spent fuel characterization

Kim, Sung-Kwan and Hong, Sung-Ahn and Son, Ho-Jin and Han, Won-Sik and Michalak, Artur and Hwang, Son-Jong and Kang, Sang-Ook (2015) Dehydrogenation of ammonia-borane by cationic Pd(II) and Ni(II) complexes in a nitromethane medium: hydrogen release and spent fuel characterization. Dalton Transactions, 44 (16). pp. 7373-7381. ISSN 1477-9226. https://resolver.caltech.edu/CaltechAUTHORS:20150529-151806306

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Abstract

A highly electrophilic cationic PdII complex, [Pd(MeCN)_4][BF_4]_2 (1), brings about the preferential activation of the B–H bond in ammonia-borane (NH3·BH3, AB). At room temperature, the reaction between 1 in CH_3NO_2 and AB in tetraglyme leads to Pd nanoparticles and formation of spent fuels of the general formula MeNH_xBO_y as reaction byproducts, while 2 equiv. of H_2 is efficiently released per AB equiv. at room temperature within 60 seconds. For a mechanistic understanding of dehydrogenation by 1, the chemical structures of spent fuels were intensely characterized by a series of analyses such as elemental analysis (EA), X-ray photoelectron spectroscopy (XPS), solid state magic-angle-spinning (MAS) NMR spectra (^2H, ^(13)C, ^(15)N, and ^(11)B), and cross polarization (CP) MAS methods. During AB dehydrogenation, the involvement of MeNO2 in the spent fuels showed that the mechanism of dehydrogenation catalyzed by 1 is different from that found in the previously reported results. This AB dehydrogenation derived from MeNO_2 is supported by a subsequent digestion experiment of the AB spent fuel: B(OMe)_3 and N-methylhydroxylamine ([Me(OH)N]_2CH_2), which are formed by the methanolysis of the AB spent fuel (MeNH_xBO_y), were identified by means of ^(11)B NMR and single crystal structural analysis, respectively. A similar catalytic behavior was also observed in the AB dehydrogenation catalyzed by a nickel catalyst, [Ni(MeCN)_6][BF_4]_2 (2).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1039/c5dt00599jDOIArticle
http://pubs.rsc.org/en/Content/ArticleLanding/2015/DT/C5DT00599JPublisherArticle
ORCID:
AuthorORCID
Hwang, Son-Jong0000-0002-3210-466X
Additional Information:© 2015 Royal Society of Chemistry. Received 10th February 2015, Accepted 10th March 2015. This work was supported by the New & Renewable Energy Core Technology Program of the Korea Institute of Energy Technology Evaluation and Planning (KETEP) granted financial resource from the Ministry of Trade, Industry & Energy, Republic of Korea (No. 20113030040020) and Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2014R1A6A1030732).
Funders:
Funding AgencyGrant Number
Korea Institute of Energy Technology Evaluation and Planning (KETEP)UNSPECIFIED
Ministry of Trade, Industry and Energy (Korea)20113030040020
National Research Foundation of KoreaNRF-2014R1A6A1030732
Issue or Number:16
Record Number:CaltechAUTHORS:20150529-151806306
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150529-151806306
Official Citation:Dehydrogenation of ammonia-borane by cationic Pd(II) and Ni(II) complexes in a nitromethane medium: hydrogen release and spent fuel characterization Sung-Kwan Kim, Sung-Ahn Hong, Ho-Jin Son, Won-Sik Han, Artur Michalak, Son-Jong Hwang and Sang Ook Kang Dalton Trans., 2015, 44, 7373-7381 DOI: 10.1039/C5DT00599J
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:57915
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:02 Jun 2015 17:06
Last Modified:03 Oct 2019 08:30

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