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 (Research - C1)
ISSN:	1099-0682
Keywords:	anion association; stereochemistry; high-pressure electrochemistry; mixed-valence; ruthenium polypyridyl
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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