6533b829fe1ef96bd128b028

RESEARCH PRODUCT

Measured and Calculated Oxidation Potentials of 1-X-12-Y-CB11Me10– Anions

Christos DouvrisJiří LudvíkMari Carmen PiquerasAbdul WahabR. CrespoJosef MichlJosef MichlJiří KlímaJan StursaMichal ValášekBrian R. SteppBrian R. Stepp

subject

Horizontal scan rateIcosahedral symmetrySubstituentElectronIonInorganic ChemistryPt electrodechemistry.chemical_compoundCrystallographychemistryComputational chemistryCarboranePhysical and Theoretical ChemistryCyclic voltammetry

description

Cyclic voltammetry of 31 icosahedral carborane anions 1-X-12-Y-CB(11)Me(10)(-) at a Pt electrode in liquid SO(2) revealed a completely reversible one-electron oxidation even at low scan rates, except for the anions with Y = I, which are oxidized irreversibly up to a scan rate of 5.0 V/s, and the anion with X = COOH and Y = H, whose oxidation is irreversible at scan rates below 1.0 V/s. Relative reversible oxidation potentials agree well with RI-B3LYP/TZVPP,COSMO and significantly less well with RI-BP86/TZVPP,COSMO or RI-HF/TZVPP,COSMO calculated adiabatic electron detachment energies. Correlations with HOMO energies of the anions are nearly as good, even though the oxidized forms are subject to considerable Jahn-Teller distortion. Except for the anion with X = F and Y = Me, the oxidation potentials vary linearly with substituent σ(p) Hammett constants. The slopes (reaction constants) are ~0.31 and ~0.55 V for positions 1 and 12, respectively.

yearjournalcountryeditionlanguage
2012-04-18Inorganic Chemistry
https://doi.org/10.1021/ic2026939