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‐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.