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Theoretical and Experimental Pathways for the Dehydrogenation of Ethylene Diamine Bisborane by an Ammonium Based Ionic Liquid

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Abstract

The current work reports both theoretical and experimental pathways for the dehydrogenation of ethylene diamine bisborane (EDAB) facilitated by tributylmethylammonium methyl sulfate ([N4441][MtSO4]). Initially, the selection of ionic liquid (IL) was made by comparing the hydrogen bond interaction energies with the experimental basicity using the quantum chemical based COSMO-RS predictions. Keeping economics in mind, [BMIM]+, [BMpyr]+, and [N4441]+ cations coupled with [OMs]−, [MtSO4]− anions were selected. This led us to the choice of tributylmethylammonium methyl sulfate ([N4441][MtSO4]) as a potential IL for the dehydrogenation reaction. The dehydrogenation experiment was then carried out at T = 105 °C and inert atmosphere, resulting in a release of 2.31 equivalents of hydrogen. The catalytic role of IL was confirmed by 1H NMR analysis. HR-MS analysis elucidated the structural integrity of IL at the end of dehydrogenation reaction and gave the final mass of the residual oligomers. 11B NMR characterization confirmed a ~2 h induction period for dehydrogenation and formation of a trigonal boron (sp2) –BH2 moiety after 150 min of reaction. Based on the dual characterization by HR-MS and 11B NMR, we propose a dehydrogenation mechanism for EDAB/[N4441][MtSO4] system under inert conditions.

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Acknowledgements

The work reported in this article was financially supported by a research Grant (SB/S3/CE/063/2013) under the Science and Engineering Research Board (SERB), Department of Science and Technology (DST), Government of India. The authors further acknowledge the Central Instrument Facility of the Indian Institute of Technology Guwahati (IIT Guwahati) and Central Instrument Facility of the Indian Institute of Science Education and Research Bhopal for providing use of their 1H and 11B NMR facilities. Due acknowledgements are also to the Analytical Laboratory within the Department of Chemistry, IIT Guwahati, for letting us record the HR-MS spectra.

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  1. Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati, Assam, 781039, India

    Debashis Kundu, G. Pugazhenthi & Tamal Banerjee

  2. Department of Chemical Engineering, Indian Institute of Science Education and Research Bhopal, Bhopal, Madhya Pradesh, 462 066, India

    Sankar Chakma

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  1. Debashis Kundu
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Correspondence to Tamal Banerjee.

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Kundu, D., Chakma, S., Pugazhenthi, G. et al. Theoretical and Experimental Pathways for the Dehydrogenation of Ethylene Diamine Bisborane by an Ammonium Based Ionic Liquid. J Solution Chem 46, 1230–1250 (2017). https://doi.org/10.1007/s10953-017-0636-5

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