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Spectroscopic Properties, Conformation and Structure of Difluorothiophosphoryl Isocyanate in the Gaseous and Solid Phase
Difluorothiophosphoryl isocyanate, F(2)P(S)NCO was characterized with UV/vis, NMR, IR (gas and Ar‐matrix), and Raman (liquid) spectroscopy. Its molecular structure was also established by means of gas electron diffraction (GED) and single crystal X‐ray diffraction (XRD) in the gas phase and solid st...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
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John Wiley and Sons Inc.
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7466015/ https://www.ncbi.nlm.nih.gov/pubmed/32908813 http://dx.doi.org/10.1002/open.202000167 |
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author | Schwabedissen, Jan Trapp, Pia C. Stammler, Hans‐Georg Mitzel, Norbert W. Wu, Zhuang Chu, Xianxu Zeng, Xiaoqing |
author_facet | Schwabedissen, Jan Trapp, Pia C. Stammler, Hans‐Georg Mitzel, Norbert W. Wu, Zhuang Chu, Xianxu Zeng, Xiaoqing |
author_sort | Schwabedissen, Jan |
collection | PubMed |
description | Difluorothiophosphoryl isocyanate, F(2)P(S)NCO was characterized with UV/vis, NMR, IR (gas and Ar‐matrix), and Raman (liquid) spectroscopy. Its molecular structure was also established by means of gas electron diffraction (GED) and single crystal X‐ray diffraction (XRD) in the gas phase and solid state, respectively. The analysis of the spectroscopic data and molecular structures is complemented by extensive quantum‐chemical calculations. Theoretically, the C (s) symmetric syn‐conformer is predicted to be the most stable conformation. Rotation about the P−N bond requires about 9 kJ mol(−1) and the predicted existence of an anti‐conformer is dependent on the quantum‐chemical method used. This syn‐orientation of the isocyanate group is the only one found in the gas phase and contained likewise in the crystal. The overall molecular structure is very similar in gas and solid, despite in the solid state the molecules arrange through intramolecular O⋅⋅⋅F contacts into layers, which are further interconnected by S⋅⋅⋅N, S⋅⋅⋅C and C⋅⋅⋅F contacts. Additionally, the photodecomposition of F(2)P(S)NCO to form CO, F(2)P(S)N, and F(2)PNCO is observed in the solid Ar‐matrix. |
format | Online Article Text |
id | pubmed-7466015 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-74660152020-09-08 Spectroscopic Properties, Conformation and Structure of Difluorothiophosphoryl Isocyanate in the Gaseous and Solid Phase Schwabedissen, Jan Trapp, Pia C. Stammler, Hans‐Georg Mitzel, Norbert W. Wu, Zhuang Chu, Xianxu Zeng, Xiaoqing ChemistryOpen Full Papers Difluorothiophosphoryl isocyanate, F(2)P(S)NCO was characterized with UV/vis, NMR, IR (gas and Ar‐matrix), and Raman (liquid) spectroscopy. Its molecular structure was also established by means of gas electron diffraction (GED) and single crystal X‐ray diffraction (XRD) in the gas phase and solid state, respectively. The analysis of the spectroscopic data and molecular structures is complemented by extensive quantum‐chemical calculations. Theoretically, the C (s) symmetric syn‐conformer is predicted to be the most stable conformation. Rotation about the P−N bond requires about 9 kJ mol(−1) and the predicted existence of an anti‐conformer is dependent on the quantum‐chemical method used. This syn‐orientation of the isocyanate group is the only one found in the gas phase and contained likewise in the crystal. The overall molecular structure is very similar in gas and solid, despite in the solid state the molecules arrange through intramolecular O⋅⋅⋅F contacts into layers, which are further interconnected by S⋅⋅⋅N, S⋅⋅⋅C and C⋅⋅⋅F contacts. Additionally, the photodecomposition of F(2)P(S)NCO to form CO, F(2)P(S)N, and F(2)PNCO is observed in the solid Ar‐matrix. John Wiley and Sons Inc. 2020-09-02 /pmc/articles/PMC7466015/ /pubmed/32908813 http://dx.doi.org/10.1002/open.202000167 Text en © 2020 The Authors. Published by Wiley-VCH GmbH This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes. |
spellingShingle | Full Papers Schwabedissen, Jan Trapp, Pia C. Stammler, Hans‐Georg Mitzel, Norbert W. Wu, Zhuang Chu, Xianxu Zeng, Xiaoqing Spectroscopic Properties, Conformation and Structure of Difluorothiophosphoryl Isocyanate in the Gaseous and Solid Phase |
title | Spectroscopic Properties, Conformation and Structure of Difluorothiophosphoryl Isocyanate in the Gaseous and Solid Phase |
title_full | Spectroscopic Properties, Conformation and Structure of Difluorothiophosphoryl Isocyanate in the Gaseous and Solid Phase |
title_fullStr | Spectroscopic Properties, Conformation and Structure of Difluorothiophosphoryl Isocyanate in the Gaseous and Solid Phase |
title_full_unstemmed | Spectroscopic Properties, Conformation and Structure of Difluorothiophosphoryl Isocyanate in the Gaseous and Solid Phase |
title_short | Spectroscopic Properties, Conformation and Structure of Difluorothiophosphoryl Isocyanate in the Gaseous and Solid Phase |
title_sort | spectroscopic properties, conformation and structure of difluorothiophosphoryl isocyanate in the gaseous and solid phase |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7466015/ https://www.ncbi.nlm.nih.gov/pubmed/32908813 http://dx.doi.org/10.1002/open.202000167 |
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