Synthesis and Application of a Perfluorinated Ammoniumyl Radical Cation as a Very Strong Deelectronator

全氟化铵基自由基阳离子的合成及其作为超强去电子剂的应用

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Abstract

The perfluorinated dihydrophenazine derivative (perfluoro-5,10-bis(perfluorophenyl)-5,10-dihydrophenazine) ("phenazine(F) ") can be easily transformed to a stable and weighable radical cation salt by deelectronation (i.e. oxidation) with Ag[Al(OR(F) )(4) ]/ Br(2) mixtures (R(F) =C(CF(3) )(3) ). As an innocent deelectronator it has a strong and fully reversible half-wave potential versus Fc(+) /Fc in the coordinating solvent MeCN (E°'=1.21 V), but also in almost non-coordinating oDFB (=1,2-F(2) C(6) H(4) ; E°'=1.29 V). It allows for the deelectronation of [Fe(III) Cp*(2) ](+) to [Fe(IV) (CO)Cp*(2) ](2+) and [Fe(IV) (CN-(t) Bu)Cp*(2) ](2+) in common laboratory solvents and is compatible with good σ-donor ligands, such as L=trispyrazolylmethane, to generate novel [M(L)(x) ](n+) complex salts from the respective elemental metals.

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