Multielectron-transfer kinetics for cis- versus trans-dioxorhenium(V) species: isoelectronic modeling with osmium(VI/V) and control of interfacial reactivity by rhenium(IV) accessibility

The mechanisms involved in the electrochemical reduction of cis- and trans-dioxorhenium(V) species in acidic and neutral solutions is reported and quantitative measurements of the accompanying electrochemical kinetics is made. Results indicate that access to Re(IV) is a significant factor in the differentiation of cis/trans electrochemical kinetics. Moreover, comparisons to isoelectronic osmium species makes possible a semiquantitative reactivity analysis.