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Titolo:
Redox characteristics and anion association behaviour of stereoisomeric forms of mono- and oligonuclear metal complexes using high pressure electrochemistry
Autore:
Yeomans, BD; Kelso, LS; Tregloan, PA; Keene, FR;
Indirizzi:
James Cook Univ N Queensland, Sch Biomed & Mol Sci, Townsville, Qld 4811, Australia James Cook Univ N Queensland Townsville Qld Australia 4811 811, Australia Univ Melbourne, Sch Chem, Parkville, Vic 3052, Australia Univ Melbourne Parkville Vic Australia 3052 arkville, Vic 3052, Australia
Titolo Testata:
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
fascicolo: 1, , anno: 2001,
pagine: 239 - 246
SICI:
1434-1948(200101):1<239:RCAAAB>2.0.ZU;2-F
Fonte:
ISI
Lingua:
ENG
Soggetto:
DIASTEREOISOMERIC FORMS; CHARGE-TRANSFER; VOLTAMMETRY; DINUCLEAR; DIRUTHENIUM(II); THERMODYNAMICS; LIGANDS;
Keywords:
anion association; stereochemistry; high-pressure electrochemistry; mixed-valence; ruthenium polypyridyl;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
30
Recensione:
Indirizzi per estratti:
Indirizzo: Keene, FR James Cook Univ N Queensland, Sch Biomed & Mol Sci, Townsville, Qld 4811, Australia James Cook Univ N Queensland Townsville Qld Australia 4811 alia
Citazione:
B.D. Yeomans et al., "Redox characteristics and anion association behaviour of stereoisomeric forms of mono- and oligonuclear metal complexes using high pressure electrochemistry", EUR J INORG, (1), 2001, pp. 239-246

Abstract

The effect of the presence of the anions PF6-, BF4-, ClO4-, and tosylate(-) on the potentials of the Ru-III/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 potentialsin the sequence PF6- < BF4- approximate to 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 PF, high-pressure electrochemical studies revealed the molar volume changes for successive redox couples in di- and trinuclear complexes were almost invariant (<Delta>V-complex = 24 +/- 2 cm(3) mol(-1)) and consistent with the valuefor mononuclear species. This constancy is interpreted in terms of isolated Ru-III/II processes in all complexes and implies that the electrostrictive effects on solvent are limited to a very short range.

ASDD Area Sistemi Dipartimentali e Documentali, Università di Bologna, Catalogo delle riviste ed altri periodici
Documento generato il 04/04/20 alle ore 12:11:52