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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Bibliographic Details
Published in:Chemistry : a European journal 2022-03, Vol.28 (14), p.e202104308-n/a
Main Authors: Shyshkov, Oleg O., Kolomeitsev, Alexander A., Hoge, Berthold, Lork, Enno, Haupt, Axel, Keßler, Mira, Röschenthaler, Gerd‐Volker
Format: Article
Language:English
Subjects:
Chemistry
Crystallography
fluorination
fluorine
hypervalent compounds
Intermediates
Magnetic resonance spectroscopy
NMR
NMR spectroscopy
Nuclear magnetic resonance
Phosphorus
Salts
Single crystals
Substitution reactions
Substrates
trifluoromethylation
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Summary: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(CF3)4], [K(18‐crown‐6)][P(CF3)3F], and [NMe4][P(CF3)2F2] were obtained by treatment of trivalent precursors with sources of CF3− or F− units. These [P(CF3)4‐nFn]− (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(CF3)4] and [K(18‐crown‐6)][P(CF3)3F] are ascertained by single crystal X‐ray crystallography. The dynamics of these compounds are investigated by variable temperature NMR spectroscopy. Different trifluoromethylated phosphoranides are accessible upon treatment of trifluoromethylated phosphanes, such as P(CF3)3, with a source of F− or CF3− in presence of a stabilizing counterion. The hypervalent compounds have been investigated by NMR spectroscopic as well as X‐ray crystallographic methods, gaining insights into their stability and structural behavior. In addition, the phosphoranides have revealed fluorinating and trifluoromethylating properties towards electrophiles.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.202104308