Nonadiabatic, short-range, intramolecular electron transfer from ruthenium(II) to cobalt(III) complexes.
The activation parameters reported for intramolecular electron-transfer between ruthenium(II) and cobalt(III) complexes have been corrected for the thermodynamic contributions of the entropy change for the reaction DeltaS0 to the entropy of activation DeltaS*, and it is concluded that these electron-transfers range from adiabatic (pyrazine bridge) to highly nonadiabatic. The electronic factors are about 20 times smaller than for diruthenium mixed-valence complexes. Spanning the metal-metal separation range of 7-14 A over which beta=0.7 A-1, the electron-transfer rates are dominated by the electronic factors, which change three times more with separation than do the nuclear factors.
Creutz
Carol
C
Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973-5000, USA.