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Synthesis, Reactivity and Structural Properties of Trifluoromethylphosphoranides
Phosphoranides are interesting hypervalent species which serve as model compounds for intermediates or transition states in nucleophilic substitution reactions at trivalent phosphorus substrates. Herein, the syntheses and properties of stable trifluoromethylphosphoranide salts are reported. [K(18‐cr...
Autores principales: | , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9305102/ https://www.ncbi.nlm.nih.gov/pubmed/35025112 http://dx.doi.org/10.1002/chem.202104308 |
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author | Shyshkov, Oleg O. Kolomeitsev, Alexander A. Hoge, Berthold Lork, Enno Haupt, Axel Keßler, Mira Röschenthaler, Gerd‐Volker |
author_facet | Shyshkov, Oleg O. Kolomeitsev, Alexander A. Hoge, Berthold Lork, Enno Haupt, Axel Keßler, Mira Röschenthaler, Gerd‐Volker |
author_sort | Shyshkov, Oleg O. |
collection | PubMed |
description | Phosphoranides are interesting hypervalent species which serve as model compounds for intermediates or transition states in nucleophilic substitution reactions at trivalent phosphorus substrates. Herein, the syntheses and properties of stable trifluoromethylphosphoranide salts are reported. [K(18‐crown‐6)][P(CF(3))(4)], [K(18‐crown‐6)][P(CF(3))(3)F], and [NMe(4)][P(CF(3))(2)F(2)] were obtained by treatment of trivalent precursors with sources of CF(3) (−) or F(−) units. These [P(CF(3))(4‐n)F(n)](−) (n=0–2) salts exhibit fluorinating (n=1–2) or trifluoromethylating (n=0) properties, which is disclosed by studying their reactivity towards selected electrophiles. The solid‐state structures of [K(18‐crown‐6)][P(CF(3))(4)] and [K(18‐crown‐6)][P(CF(3))(3)F] are ascertained by single crystal X‐ray crystallography. The dynamics of these compounds are investigated by variable temperature NMR spectroscopy. |
format | Online Article Text |
id | pubmed-9305102 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-93051022022-07-28 Synthesis, Reactivity and Structural Properties of Trifluoromethylphosphoranides Shyshkov, Oleg O. Kolomeitsev, Alexander A. Hoge, Berthold Lork, Enno Haupt, Axel Keßler, Mira Röschenthaler, Gerd‐Volker Chemistry Research Articles Phosphoranides are interesting hypervalent species which serve as model compounds for intermediates or transition states in nucleophilic substitution reactions at trivalent phosphorus substrates. Herein, the syntheses and properties of stable trifluoromethylphosphoranide salts are reported. [K(18‐crown‐6)][P(CF(3))(4)], [K(18‐crown‐6)][P(CF(3))(3)F], and [NMe(4)][P(CF(3))(2)F(2)] were obtained by treatment of trivalent precursors with sources of CF(3) (−) or F(−) units. These [P(CF(3))(4‐n)F(n)](−) (n=0–2) salts exhibit fluorinating (n=1–2) or trifluoromethylating (n=0) properties, which is disclosed by studying their reactivity towards selected electrophiles. The solid‐state structures of [K(18‐crown‐6)][P(CF(3))(4)] and [K(18‐crown‐6)][P(CF(3))(3)F] are ascertained by single crystal X‐ray crystallography. The dynamics of these compounds are investigated by variable temperature NMR spectroscopy. John Wiley and Sons Inc. 2022-02-09 2022-03-07 /pmc/articles/PMC9305102/ /pubmed/35025112 http://dx.doi.org/10.1002/chem.202104308 Text en © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Research Articles Shyshkov, Oleg O. Kolomeitsev, Alexander A. Hoge, Berthold Lork, Enno Haupt, Axel Keßler, Mira Röschenthaler, Gerd‐Volker Synthesis, Reactivity and Structural Properties of Trifluoromethylphosphoranides |
title | Synthesis, Reactivity and Structural Properties of Trifluoromethylphosphoranides |
title_full | Synthesis, Reactivity and Structural Properties of Trifluoromethylphosphoranides |
title_fullStr | Synthesis, Reactivity and Structural Properties of Trifluoromethylphosphoranides |
title_full_unstemmed | Synthesis, Reactivity and Structural Properties of Trifluoromethylphosphoranides |
title_short | Synthesis, Reactivity and Structural Properties of Trifluoromethylphosphoranides |
title_sort | synthesis, reactivity and structural properties of trifluoromethylphosphoranides |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9305102/ https://www.ncbi.nlm.nih.gov/pubmed/35025112 http://dx.doi.org/10.1002/chem.202104308 |
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