Journal of Electroanalytical Chemistry, Vol.689, 257-261, 2013
Isoflurane as a solvent for electrochemistry. Electrooxidation study of icosahedral carborane anions in four different solvents
Voltammetric studies of icosahedral carborane anions CB11Me12- (1), 1-H-CB11Me11- (2), 1-H-12-H-CB11Me10- (3), and 1-H-12-I-CB11Me10- (4) are reported in isoflurane (1-chloro-2,2,2-trifluoroethyl difluoromethyl ether) and in three other solvents with different polarity (liquid SO2, acetonitrile, dichloromethane). They demonstrate the first use of isoflurane as a non-polar electrochemical solvent. The anions 1,2 and 3 show reversible one-electron oxidations in all four solvents, whereas the oxidation of 4 is irreversible even at high scan rates. The measured half-wave potentials (E-1/2) show a remarkable variation in the four different solvents. The E-1/2 values are discussed in terms of specific solvation of the anions. The experimental results correlate fairly well with density functional theory (DFT) calculations. (C) 2012 Elsevier B.V. All rights reserved.
Keywords:Isoflurane;Relative permittivity;Icosahedral carborane anions;Electrochemical oxidation;Voltammetry;Aprotic media