Synthesis and Application of a Perfluorinated Ammoniumyl Radical Cation as a Very Strong Deelectronator
- PMID: 32187797
- PMCID: PMC7317951
- DOI: 10.1002/anie.202002768
Synthesis and Application of a Perfluorinated Ammoniumyl Radical Cation as a Very Strong Deelectronator
Abstract
The perfluorinated dihydrophenazine derivative (perfluoro-5,10-bis(perfluorophenyl)-5,10-dihydrophenazine) ("phenazineF ") can be easily transformed to a stable and weighable radical cation salt by deelectronation (i.e. oxidation) with Ag[Al(ORF )4 ]/ Br2 mixtures (RF =C(CF3 )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-F2 C6 H4 ; E°'=1.29 V). It allows for the deelectronation of [FeIII Cp*2 ]+ to [FeIV (CO)Cp*2 ]2+ and [FeIV (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.
Keywords: Iron complexes; main-group chemistry; oxidizing agents (deelectronators); radical ions; weakly coordinating anions.
© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
Conflict of interest statement
The authors declare no conflict of interest.
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- Here and in the following we use the particle-based view on the classical oxidation=deelectronation and reduction=electronation processes. Thus, an oxidant is a deelectronator and a reductant an electronator. This evolved from our work on the protoelectric potential map (PPM) for keeping with the successful and self-explaining acid–base picture. Thus, the equivalent to a deprotonation reaction is a deelectronation reaction. This is in keeping with earlier textbook suggestions by Bockris and Reddy and follows our concept paper on the PPM (Ref. [1 b]) and the recent Review (Ref. [1 c]);
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- Bockris J. O.’M., Reddy A. K. N., Modern Electrochemistry 1. Ionics, Kluwer Academic Publishers, Boston, MA, 2002.
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