Cargando…

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...

Descripción completa

Detalles Bibliográficos
Autores principales: Schwabedissen, Jan, Trapp, Pia C., Stammler, Hans‐Georg, Mitzel, Norbert W., Wu, Zhuang, Chu, Xianxu, Zeng, Xiaoqing
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2020
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
_version_ 1783577714769264640
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
work_keys_str_mv AT schwabedissenjan spectroscopicpropertiesconformationandstructureofdifluorothiophosphorylisocyanateinthegaseousandsolidphase
AT trapppiac spectroscopicpropertiesconformationandstructureofdifluorothiophosphorylisocyanateinthegaseousandsolidphase
AT stammlerhansgeorg spectroscopicpropertiesconformationandstructureofdifluorothiophosphorylisocyanateinthegaseousandsolidphase
AT mitzelnorbertw spectroscopicpropertiesconformationandstructureofdifluorothiophosphorylisocyanateinthegaseousandsolidphase
AT wuzhuang spectroscopicpropertiesconformationandstructureofdifluorothiophosphorylisocyanateinthegaseousandsolidphase
AT chuxianxu spectroscopicpropertiesconformationandstructureofdifluorothiophosphorylisocyanateinthegaseousandsolidphase
AT zengxiaoqing spectroscopicpropertiesconformationandstructureofdifluorothiophosphorylisocyanateinthegaseousandsolidphase