Redox characteristics and anion association behaviour of stereoisomeric forms of mono- and oligonuclear metal complexes using high pressure electrochemistry

Yeomans, Brett D., Kelso, Laurence S., Tregloan, Peter A., and Keene, F. Richard (2001) Redox characteristics and anion association behaviour of stereoisomeric forms of mono- and oligonuclear metal complexes using high pressure electrochemistry. European Journal of Inorganic Chemistry, 2001 (1). pp. 239-246.

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Abstract

The effect of the presence of the anions PF6 -, BF4 -, ClO4 -, and tosylate- on the potentials of the RuIII/II redox processes in a series of mono-, di-, and trinuclear complexes involving polypyridyl ligands are reported. The anions gives rise to a cathodic shift in the respective redox potentials in the sequence PF6 - , BF4 - ø ClO4 - , tos-, with the magnitude of the shifts being largest for the tri-nuclear and smallest for the mononuclear species. In one dinuclear complex, a variation of anion was also observed to affect the difference in potentials between the [6+/5+] and [5+/4+] couples. These effects are consistent with known specific association of the anions with metal complexes of this type. In the presence of PF6 -, high-pressure electrochemical studies revealed the molar volume changes for successive redox couples in di- and rinuclear complexes were almost invariant (ÄVcomplex = 24 ±2 cm3 mol-1) and consistent with the value for mononuclear species. This constancy is interpreted in terms of isolated RuIII/II processes in all complexes and implies that the electrostrictive effects on solvent are limited to a very short range.

Item ID: 8471
Item Type: Article (Refereed Research - C1)
Keywords: anion association; stereochemistry; high-pressure electrochemistry; mixed-valence; ruthenium polypyridyl
ISSN: 1099-0682
Funders: ARC
Date Deposited: 18 Feb 2010 00:46
FoR Codes: 03 CHEMICAL SCIENCES > 0302 Inorganic Chemistry > 030207 Transition Metal Chemistry @ 100%
SEO Codes: 97 EXPANDING KNOWLEDGE > 970103 Expanding Knowledge in the Chemical Sciences @ 100%
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