Transport, ionic conductivity, and viscosity properties of the metal complex molten salt [Co(bpy(CO(2)MePEG-350)(2))(3)](ClO4)(2) (MePEG = monomethyl-terminated polyether, average MW = 350) are strongly affected by dissolution of LiClO4 electrolyte in the melt. The physical self-diffusion of the [Co(bpy(CO(2)MePEG-350)(2))(3)](2+) and the rate of [Co(bpy(CO(2)MePEG-350)(2))(3)](2+/+) electron self-exchange are slowed, the melt Viscosity increased and ionic conductivity decreased, and thermal activation barriers for all are enhanced by increasing [LiClO4]. Most of the effects are associated with the Li+ cation/polyether coordination well-known in polymer electrolytes, in which chain cross-linking and a decrease in chain segmental mobility occurs. The [Co(bpy(CO(2)MePEG-350)2)(3)](2+/+) electron self-exchange reaction is shown to be adiabatic (kinetic prefactor cn. 10(13) s(-1)), and modest changes in its rate with [LiClO4] are caused by changes in the electron transfer barrier energy. The results ate used to draw a hierarchy of dynamics in the metal complex melt in which, for [LiClO4] = 1.3 M, the average diffusive jump rate is ca. 3 s(-1), the average electron hopping rate is ca. 2 x 10(4) s(-1), and the rate of short-range motions of the hard metal complex core within its soft polyether shell (producing adjacent core-core contacts) is ca. greater than or equal to 10(5) s(-1).