Electrochemical and Spectroscopic Studies of Polypyridine Complexes of Fe(II)/(III) and Ru(II)/(III) in the Aluminum Chloride: N-(1-Butyl)Pyridinium Chloride Molten Salt.
STATE UNIV OF NEW YORK AT BUFFALO DEPT OF CHEMISTRY
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The electrochemical and spectroscopic behavior of Febpy32, Fephen32 and Rubpy32 in an ambient-temperature molten salt system, aluminum chlorideN-l-butylpyridinium chloride BuPyCl have been studied as a function of melt composition. The complexes show a single one-electron reversible oxidation wave from melt compositions of 11 to 21 AlCl3BuPyCl mole ratio. Visible spectroscopic and electrochemical data indicate that these compounds are stable in the neutral 11 and acid mole ratio greater than 1 melts, while Rubpy32 is stable in basic melts mole ratio less than 1, but Febpy32 and Fephen32 decompose to FeCl42-. Comparison of the formal potentials for MIIIII-polypyridine couples studied here and in other solvents indicate that the redox properties of these complexes are relatively insensitive to the nature of the solvent. It was shown that oxygen acts as an oxidant in the acid melts to oxidize Febpy32, Fephen32 and Rubpy32 to their corresponding 3 form. The 3 form of each complex was stable in acid melts for several weeks. Perchlorate is also shown to function as an oxidant in acidic melts. Author
- Inorganic Chemistry
- Atomic and Molecular Physics and Spectroscopy