Two-equivalent electrochemical reduction of a cyano-complex Tl-III(CN)(2) (+) and the novel di-nuclear compound (CN)(5)Pt-II-Tl-III (0)
2005 (English)In: Electrochimica Acta, ISSN 0013-4686, E-ISSN 0019-4686, Vol. 50, no 22, 4444-4450 p.Article in journal (Refereed) Published
Extending our recent insights in two-electron transfer microscopic mechanisms for a Tl-III/Tl-I redox system, the electrochemical response of glassy carbon electrode in acidified solutions of Tl-III (ClO4)(3) containing different concentrations of sodium cyanide has been extensively studied for the first time by use of cyclic voltammetry and the CVSIM curve simulation PC program. The complex [Tl-III(CN)(2)](+) has been thoroughly identified electrochemically and shown to display a single welldefined reduction wave (which has no anodic counterpart), ascribed to the two-equivalent process yielding [Tl-I(aq)](+). This behavior is similar to that of [Tl-III (aq)](3+) ion in the absence of sodium cyanide, disclosed in the previous work, and is compatible with the quasi-simultaneous yet sequential two-electron transfer pattern (with two reduction waves merged in one), implying the rate-determining first electron transfer step (resulting in the formation of a covalently interacting di-thallium complex as a metastable intermediate), and the fast second electron transfer step. Some preliminary studies of the two-equivalent reduction of directly metal-metal bonded stable compound [(CN)(5)Pt-II-Tl-III](0) has been also performed displaying two reduction waves compatible with a true sequential pattern.
Place, publisher, year, edition, pages
2005. Vol. 50, no 22, 4444-4450 p.
thallium(III), cyano-complexes, two-electron transfer, cyclic voltammetry, di-nuclear complexes, metal-metal bond, stationary electrode polarography, platinum-thallium compounds, 2-electron transfer, aqueous-solution, molybdenum, mechanisms, systems
IdentifiersURN: urn:nbn:se:kth:diva-14986DOI: 10.1016/j.electacta.2005.02.006ISI: 000231353800013ScopusID: 2-s2.0-23144464502OAI: oai:DiVA.org:kth-14986DiVA: diva2:333027
QC 201005252010-08-052010-08-05Bibliographically approved