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Anodic oxidation of organometallic sandwich complexes using [Al(OC(CF3)(3))(4)](-) or [AsF6](-) as the supporting electrolyte anion

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Author(s)

  • Michael P. Stewart
  • Lacey Marina Paradee
  • Ines Raabe
  • Nils Trapp
  • John M. Slattery
  • Ingo Krossing
  • William E. Geiger
  • John Martin Slattery

Department/unit(s)

Publication details

JournalJOURNAL OF FLUORINE CHEMISTRY
DatePublished - Nov 2010
Issue number11
Volume131
Number of pages5
Pages (from-to)1091-1095
Original languageEnglish

Abstract

Anodic voltammetry and electrolysis of the metallocenes ferrocene ruthenocene and nickelocene have been studied in dichloromethane containing two different fluorine-containing anions in the supporting electrolyte The perfluoroalkoxyaluminate anion [Al(OC(CF3)(3))(4)](-) has very low nucleophilicity as shown by its inertness towards the strong electrophile [RuCp2](+) and by computation of Its electrostatic potential in comparison to other frequently used electrolyte anions The low ion-pairing ability of this anion was shown by the large spread in E-1/2 potentials (Delta E-1/2 = 769 mV) for the two one-electron oxidations of bis(fulvalene)dinickel The hexafluoroarsenate inion [AsF6](-) on the other hand reacts rapidly with the ruthenocenium ion and is much more strongly ion-pairing towards oxidized bis(fulvalene)dinickel (Delta E-1/2 = 492 mV) In terms of applications of these two anions to the anodic oxidation of organometallic sandwich complexes the behavior of [Al(OC(CF3)(3))(4)](-) is similar to that of other weakly-coordinating anions such as [B(C6F5)(4)](-) whereas that of [AsF6](-) is similar to the more traditional electrolyte anions such as [PF6](-) and [BF4](-) Additionally the synthesis and crystal structure of [Cp2Fe][Al(OC(CF3)(3))(4)] are reported (C) 2010 Elsevier BV All rights reserved

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