Configurational and conformational effects on electron transfer rates
Abstract
Electron transfer rate constants of the cage complexes Λ, Δ, fac, mer-[Co{(NH3)2, Me3sar}]5+/4+[where {(NH3)2, Me3sar}=(4R,12R,17R) or (4R,11R,17R)-trimethyl-3,6,10,13,16,19 -hexa-azabicyclo[6.6.6]icosane-1,8-diamine or the catoptric (S) forms] show >103-fold differences for these very similar diastereoisomeric ions which are ascribed primarily to lel–ob conformational changes and their effect on the redox potentials of the couples as well as on the electron transfer rates.