Abstract
The recent interest in the voltammetry of the dioxorhenium(V) complexes of pyridine prompted us to investigate the voltammetry of μ-oxo-bis[cis-dichloro-cis-dipyridyloxorhenium(V)] complexes. Seven compounds containing pyridines with electron-withdrawing or electron-donating substituents were synthesized and their redox behavior characterized by variable potential sweep rate cyclic voltammetry and variable pulse height differential pulse voltammetry. Four one-electron redox couples are observed within the accessible potential range of CH2Cl2 containing 0.10 M n-Bu4NPF6 as the supporting electrolyte. The dimeric structure remains intact for the two oxidation and first reduction processes. The complex undergoes a reversible heterolytic cleavage of the μ-oxo linkage following the second reduction process. The redox potential for each process correlates with the inductive effect of the pyridyl substituent.
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