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Experimental and theoretical evidence of dihydrogen bonds in lithium amidoborane
In situ high-pressure synchrotron X-ray diffraction, Raman scattering, and complementary first-principles calculations have revealed that structural and spectroscopic properties of lithium amidoborane compound are largely determined by multiple heteropolar dihydrogen bonds. The crystal structure of...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7567059/ https://www.ncbi.nlm.nih.gov/pubmed/33060733 http://dx.doi.org/10.1038/s41598-020-74654-0 |
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author | Magos-Palasyuk, Ewelina Litwiniuk, Aleksander Palasyuk, Taras |
author_facet | Magos-Palasyuk, Ewelina Litwiniuk, Aleksander Palasyuk, Taras |
author_sort | Magos-Palasyuk, Ewelina |
collection | PubMed |
description | In situ high-pressure synchrotron X-ray diffraction, Raman scattering, and complementary first-principles calculations have revealed that structural and spectroscopic properties of lithium amidoborane compound are largely determined by multiple heteropolar dihydrogen bonds. The crystal structure of the compound is stabilized by dimeric complexes, wherein molecular ions bind together by intermolecular dihydrogen bonds of unconventional type. This strong intermolecular coupling determines stable character of the crystal structure in the pressure range up to ~ 30 GPa and is spectroscopically manifested by pronounced changes related to molecular vibrations of the amino group: the splitting of stretching modes, the anomalous behavior of wagging modes as well as Fermi resonance due to vibrational coupling of bending and stretching modes, significantly enhanced above 10 GPa. Unconventional nature of dihydrogen bonds is confirmed by the frequency increase, blueshift, of NH stretching modes with pressure. A role of certain hydrogen mediated interactions in the process of dehydrogenation of ammonia borane and its alkali metal derivatives is speculated. Findings presented here call for reconsideration of hydrogen release mechanism from alkali metal ammonia borane derivatives. The work makes significant contribution towards establishing the general theory of ubiquitous and versatile hydrogen mediated interactions. |
format | Online Article Text |
id | pubmed-7567059 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-75670592020-10-19 Experimental and theoretical evidence of dihydrogen bonds in lithium amidoborane Magos-Palasyuk, Ewelina Litwiniuk, Aleksander Palasyuk, Taras Sci Rep Article In situ high-pressure synchrotron X-ray diffraction, Raman scattering, and complementary first-principles calculations have revealed that structural and spectroscopic properties of lithium amidoborane compound are largely determined by multiple heteropolar dihydrogen bonds. The crystal structure of the compound is stabilized by dimeric complexes, wherein molecular ions bind together by intermolecular dihydrogen bonds of unconventional type. This strong intermolecular coupling determines stable character of the crystal structure in the pressure range up to ~ 30 GPa and is spectroscopically manifested by pronounced changes related to molecular vibrations of the amino group: the splitting of stretching modes, the anomalous behavior of wagging modes as well as Fermi resonance due to vibrational coupling of bending and stretching modes, significantly enhanced above 10 GPa. Unconventional nature of dihydrogen bonds is confirmed by the frequency increase, blueshift, of NH stretching modes with pressure. A role of certain hydrogen mediated interactions in the process of dehydrogenation of ammonia borane and its alkali metal derivatives is speculated. Findings presented here call for reconsideration of hydrogen release mechanism from alkali metal ammonia borane derivatives. The work makes significant contribution towards establishing the general theory of ubiquitous and versatile hydrogen mediated interactions. Nature Publishing Group UK 2020-10-15 /pmc/articles/PMC7567059/ /pubmed/33060733 http://dx.doi.org/10.1038/s41598-020-74654-0 Text en © The Author(s) 2020 Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. |
spellingShingle | Article Magos-Palasyuk, Ewelina Litwiniuk, Aleksander Palasyuk, Taras Experimental and theoretical evidence of dihydrogen bonds in lithium amidoborane |
title | Experimental and theoretical evidence of dihydrogen bonds in lithium amidoborane |
title_full | Experimental and theoretical evidence of dihydrogen bonds in lithium amidoborane |
title_fullStr | Experimental and theoretical evidence of dihydrogen bonds in lithium amidoborane |
title_full_unstemmed | Experimental and theoretical evidence of dihydrogen bonds in lithium amidoborane |
title_short | Experimental and theoretical evidence of dihydrogen bonds in lithium amidoborane |
title_sort | experimental and theoretical evidence of dihydrogen bonds in lithium amidoborane |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7567059/ https://www.ncbi.nlm.nih.gov/pubmed/33060733 http://dx.doi.org/10.1038/s41598-020-74654-0 |
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