Issue 16, 2015

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

Abstract

A highly electrophilic cationic PdII complex, [Pd(MeCN)4][BF4]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 CH3NO2 and AB in tetraglyme leads to Pd nanoparticles and formation of spent fuels of the general formula MeNHxBOy as reaction byproducts, while 2 equiv. of H2 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, 13C, 15N, and 11B), 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 MeNO2 is supported by a subsequent digestion experiment of the AB spent fuel: B(OMe)3 and N-methylhydroxylamine ([Me(OH)N]2CH2), which are formed by the methanolysis of the AB spent fuel (MeNHxBOy), were identified by means of 11B 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][BF4]2 (2).

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

Supplementary files

Article information

Article type
Paper
Submitted
10 Feb 2015
Accepted
10 Mar 2015
First published
10 Mar 2015

Dalton Trans., 2015,44, 7373-7381

Author version available

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

S. Kim, S. Hong, H. Son, W. Han, A. Michalak, S. Hwang and S. O. Kang, Dalton Trans., 2015, 44, 7373 DOI: 10.1039/C5DT00599J

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