Here we present the syntheses of non-coordinated electron-rich phenolate anions via deprotonation of the corresponding alcohols with an extremely powerful perethyl tetraphosphazene base (Schwesinger base). The application of uncharged phosphazenes renders the selective preparation of anionic phenol-phenolate and phenolate hydrates possible, which allows the investigation of hydrogen bonding in these species. Hydrogen bonding brings about decreased redox potentials relative to the corresponding non-coordinated phenolate anions. The latter show redox potentials of up to -0.72(1)V vs. SCE, which is comparable to that of zinc metal, thus qualifying their application as organic zinc mimics. We utilized phenolates as reducing agents for the generation of radical anions in addition to the corresponding phenoxyl radicals. A tetracyanoethylene radical anion salt was synthesized and fully characterized as a representative example. We also present the activation of sulfur hexafluoride (SF 6 ) with phenolates in an SET reaction. Thereby the nature of the respective phenolate determines whether simple fluorides or pentafluorosulfanide ([SF 5 ] - ) salts are formed. © 2020 Wiley-VCH GmbH.
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