Phosphorus-fluorine chemistry. XIII. The adduct of nitrosyl fluoride with phenyltetrafluorophosphorane. New fluorophosphates

Article abstract of DOI:10.1021/ic50024a014

Nitrosyl fluoride was found to react with phenyltetrafluorophosphorane to form a solid, thermally unstable 1:1 adduct. Evidence for the formulation of this adduct as a nitrosyl salt, NO⁺C₆H₅PF₅^-, based on various chemical reactions, is presented. The novel fluoroanions, R(Ar)PF₅^-, together with alkyl(aryl)dialkylaminotrifluorophosphoranes, R(Ar)PF₃NR₂, are also obtained in the form of stable dialkylammonium salts upon dialkylaminolysis of tetrafluorophosphoranes, R(Ar)PF₄. The stereochemistry of the R(Ar)PF₅^- anions, and of the alkyl(aryl)dialkylaminotrifluorophosphoranes, based on n.m.r. spectroscopic studies, is discussed. In contrast to nitrosyl fluoride, nitryl fluoride reacted with phenyltetrafluorophosphorane with direct nitration of the aromatic ring.