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

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

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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

Original languageEnglish
Pages (from-to)1091-1095
Number of pages5
Issue number11
Publication statusPublished - Nov 2010

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