Heterogeneous Rate Constants of the Electron-Transfer of Iron- and Ruthenium-bipyridine Complexes in Imidazolium-Based Ionic Liquids

Abstract

The heterogeneous rate constants (ks) for the oxidation of iron- and ruthenium-bipyridine complexes, [Fe(bpy)3]²⁺/³⁺ and [Ru(bpy)3]²⁺/³⁺ have been determined using Nicholson's method in imidazolium-based ionic liquids with five different types of cation/anion over a range of temperature from 298–318 K. The heterogeneous rate constants of these redox reactions range from 10⁻⁴ to 10⁻³ cm s⁻¹, depending on the dynamic viscosity and type of cation/anion of the ILs. Marcus-Hush theory is used to explain the activation energies, Ea. Similar activation energies are found for the Fe-bipyridine and Ru-bipyridine complexes indicating that inner-sphere reorganization energy has only a small influence. For the calculation of the solvent-dependent outer sphere reorganization energy a dipole-free expression is used, adopted to the different dielectric properties of ionic liquids compared to organic solvents. i-Ru drops have been compensated using the corresponding experimental uncompensated Ru-values obtained from temperature dependent Bode-plots.