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.
Abstract
The electrochemical and spectroscopic behavior of Fe(bpy)3(2+), Fe(phen)3(2+) and Ru(bpy)3(2+) in an ambient-temperature molten salt system, aluminum chloride:N-(l-butyl)pyridinium 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 1:1 to 2:1 (AlCl3:BuPyCl mole ratio). Visible spectroscopic and electrochemical data indicate that these compounds are stable in the neutral (1:1) and acid (mole ratio greater than 1) melts, while Ru(bpy)3(2+) is stable in basic melts (mole ratio less than 1), but Fe(bpy)3(2+) and Fe(phen)3(2+) decompose to FeCl4(2-). Comparison of the formal potentials for M(III)/(II)-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 Fe(bpy)3(2+), Fe(phen)3(2+) and Ru(bpy)3(2+) 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)
Document Details
- Document Type
- Technical Report
- Publication Date
- Jan 01, 1984
- Accession Number
- ADA139170
Entities
People
- R. A. Osteryoung
- S. Sahami
Organizations
- University at Buffalo