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

作者：Stewart Michael P; Paradee Lacey Marina; Raabe Ines; Trapp Nils; Slattery John S; Krossing Ingo; Geiger William E^*

来源：Journal of Fluorine Chemistry, 2010, 131(11): 1091-1095.

DOI：10.1016/j.jfluchem.2010.03.001

• Electrochemistry
• Nickelocene
• Ruthenocene
• Weakly-coordinating anions
• Ion pairing
• Fluoroalkoxyaluminate anion
• Hexafluoroarsenate
• Traditional anions
• Nucleophilicity

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 th

• 出版日期2010-11