摘要: We have been exploring the proton-coupled reductions of various dioxorhenium(V) species because of the more general insights they provide into the kinetics and thermodynamics of multielectron transfer processes. The rhenium (V) co... 展开 We have been exploring the proton-coupled reductions of various dioxorhenium(V) species because of the more general insights they provide into the kinetics and thermodynamics of multielectron transfer processes. The rhenium (V) complexes are also amenable, however, to proton-decoupled one-electron oxidation-both optically (via metal-to-ligand charge-transfer excitation; Our prior studies of electron transfer (ET) thermodynamics revealed a strong dependence of the Re (VI/V) formal potential on ligand substituent characteristics (most notably, substituent electron donating or withdrawing characteristics). The studies also showed-independent of ligand substituent identify-a strong dependence of E (sub f) on isomeric form cis versus trans coordination geometry. In all cases the cis form was more easily oxidize than the corresponding trans, generally by about 600mV. 收起