Reactions in [²H]₃-acetonitrile between trimethyl phosphite copper(I) or iron(II) cations and phosphorus pentafluoride or tungsten hexafluoride

Fluorination of trimethyl phosphite in reactions between phosphorus pentafluoride or tungsten hexafluoride and the cations Cu[P(OMe)<sub>3</sub>]<sub>4</sub><sup>+</sup> or [Fe{P(OMe)<sub>3</sub>}<sub>n</sub>(NCMe)<sub>6−n</sub>]<sup>2+</sup>, n=5 or 4, in [<sup>2</sup>H]<sub>3</sub>-acetonitrile is influenced both by the metal and by the solvent. Mixtures of phosphorus(III and V) and tungsten(VI) fluorides are obtained whose origin can be understood in terms of kinetic control by Cu<sup>I</sup> or Fe<sup>II</sup>, labile and inert towards substitution respectively, and the Lewis base properties of CD<sub>3</sub>CN. <sup>19</sup>F and <sup>31</sup>P n.m.r. spectroscopy was used to study the reactions and the n.m.r. parameters of PF<sub>5</sub>·P(OMe)<sub>3</sub> are reported