TY - JOUR
T1 - Anodic oxidation of organometallic sandwich complexes using [Al(OC(CF3)(3))(4)](-) or [AsF6](-) as the supporting electrolyte anion
AU - Stewart, Michael P.
AU - Paradee, Lacey Marina
AU - Raabe, Ines
AU - Trapp, Nils
AU - Slattery, John M.
AU - Krossing, Ingo
AU - Geiger, William E.
AU - Slattery, John Martin
PY - 2010/11
Y1 - 2010/11
N2 - 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
AB - 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
UR - http://www.scopus.com/inward/record.url?scp=77954850918&partnerID=8YFLogxK
U2 - 10.1016/j.jfluchem.2010.03.001
DO - 10.1016/j.jfluchem.2010.03.001
M3 - Article
SN - 0022-1139
VL - 131
SP - 1091
EP - 1095
JO - JOURNAL OF FLUORINE CHEMISTRY
JF - JOURNAL OF FLUORINE CHEMISTRY
IS - 11
ER -