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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...

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Autores principales: Shyshkov, Oleg O., Kolomeitsev, Alexander A., Hoge, Berthold, Lork, Enno, Haupt, Axel, Keßler, Mira, Röschenthaler, Gerd‐Volker
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2022
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.
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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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