Preparation of the solvated iron(II) cation in acetonitrile using high oxidation-state fluorides and its reaction with trimethyl phosphite

Abstract
The cation [Fe(NCMe)6]2+ is formed from reactions in acetonitrile of iron metal with WF6, MoF6, PF5, or the NO+ cation and from the reaction of iron(II) fluoride with PF5. Oxidation to FeIII is not observed using binary fluorides or NO+, but [Fe(NCMe)6]2+ is oxidised by chlorine in MeCN to give the tetrachloroferrate(III) anion. The MeCN co-ordinated to FeII is replaced by trimethyl phosphite giving [Fe(NCMe){P(OMe)3}5]2+ as the final product at room temperature. Some of the intermediate complexes in this reaction have been identified in solution by 31P{1H} n.m.r. spectroscopy.

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