Ingram, DJ;
Headen, TF;
Skipper, NT;
Callear, SK;
Billing, M;
Sella, A;
(2018)
Dihydrogen: Vs. hydrogen bonding in the solvation of ammonia borane by tetrahydrofuran and liquid ammonia.
Physical Chemistry Chemical Physics
, 20
(17)
pp. 12200-12209.
10.1039/c7cp08220g.
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Abstract
The solvation structures of two systems rich in hydrogen and dihydrogen bonding interactions have been studied in detail experimentally through neutron diffraction with hydrogen/deuterium isotopic substitution. The results were analysed by an atomistic Monte Carlo simulation employing refinement to the experimental scattering data. The systems studied were the hydrogen storage material ammonia borane (NH 3 BH 3 , AB) dissolved in tetrahydrofuran (THF), and liquid ammonia (NH 3 ), the latter in which AB shows unusually high solubility (260 g AB per 100 g NH 3 ) and potential regeneration properties. The full orientational and positional manner in which AB-AB, AB-THF and AB-NH 3 pairs interact with each other were successfully deciphered from the wide Q-range total neutro n scattering data. This provided an unprecedented level of detail into such highly (di)hydrogen bonding solute-solvent interactions. In particular this allowed insight into the way in which H-B acts as a hydrogen bond acceptor. The (di)hydrogen bonding was naturally determined to dictate the intermolecular interactions, at times negating the otherwise expected tendency for polar molecules to align themselves with anti-parallel dipole moments. Several causes for the extreme solubility of AB in ammonia were determined, including the ability of ammonia to (di)hydrogen bond to both ends of the AB molecule and the small size of the ammonia molecule relative to AB and THF. The AB B-H to ammonia H dihydrogen bond was found to dominate the intermolecular interactions, occurring almost three times more often than any other hydrogen or dihydrogen bond in the system. The favourability of this interaction was seen on the bulk scale by a large decrease in AB clustering in ammonia compared to in the dihydrogen bond-less THF.
| Type: | Article |
|---|---|
| Title: | Dihydrogen: Vs. hydrogen bonding in the solvation of ammonia borane by tetrahydrofuran and liquid ammonia |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1039/c7cp08220g |
| Publisher version: | https://doi.org/10.1039/c7cp08220g |
| Language: | English |
| Additional information: | This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10049238 |
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