TY - JOUR
T1 - Electrooxidation of [(eta5-C5H5)Fe(CO)2]2 as a probe of the nucleophilic properties of ionic liquid anions
AU - Torriero, Angel Alberto Jesus
AU - Shiddiky, Muhammad Johirul Alam
AU - Bullock, John P
AU - Boas, John Frank
AU - Macfarlane, Douglas Robert
AU - Bond, Alan Maxwell
PY - 2010
Y1 - 2010
N2 - The oxidative electrochemistry of [CpFe(CO)(2)](2), 1 (CP = [eta(5)-C5H5](-)), was examined in detail in ionic liquids (ILs) composed of ions of widely varying Lewis acid-base properties. Cyclic voltammetric responses were strongly dependent on the nucleophilic properties of the IL anion, but all observations are consistent with the initial formation of 1(+) followed by attack from the IL anion. In [NTf2](-)-based ILs ([NTf2](-)=bis(trifluoromethylsulfonyl)amide), the process shows nearly ideal chemical reversibility as the reaction between 1(+) and [NTf2] is very slow. This is highly significant, as 1(+) is known to be highly susceptible to nucleophilic attack and its stability indicates a remarkable lack of coordinating ability of these ILs. In 1-methyl-3-butylimidazolium hexafluorophosphate, [bmim][PF6], the oxidation of 1 is still largely reversible, but there is more pronounced evidence of [PF6](-) coordination. In contrast, 1 exhibits an irreversible two-electron oxidation process in a dicyanamide-based IL.
AB - The oxidative electrochemistry of [CpFe(CO)(2)](2), 1 (CP = [eta(5)-C5H5](-)), was examined in detail in ionic liquids (ILs) composed of ions of widely varying Lewis acid-base properties. Cyclic voltammetric responses were strongly dependent on the nucleophilic properties of the IL anion, but all observations are consistent with the initial formation of 1(+) followed by attack from the IL anion. In [NTf2](-)-based ILs ([NTf2](-)=bis(trifluoromethylsulfonyl)amide), the process shows nearly ideal chemical reversibility as the reaction between 1(+) and [NTf2] is very slow. This is highly significant, as 1(+) is known to be highly susceptible to nucleophilic attack and its stability indicates a remarkable lack of coordinating ability of these ILs. In 1-methyl-3-butylimidazolium hexafluorophosphate, [bmim][PF6], the oxidation of 1 is still largely reversible, but there is more pronounced evidence of [PF6](-) coordination. In contrast, 1 exhibits an irreversible two-electron oxidation process in a dicyanamide-based IL.
UR - http://www.scopus.com/record/display.url?eid=2-s2.0-77649096187&origin=inward&txGid=l9kwAZQzvFLnV9vIm5CqLHm%3a16
UR - https://www.scopus.com/pages/publications/77649096187
U2 - 10.1021/ic9025238
DO - 10.1021/ic9025238
M3 - Article
SN - 0020-1669
VL - 49
SP - 2502
EP - 2511
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 5
ER -