The decomposition and formation of the platinum-thallium bond in the (CN)(5)Pt-Tl(edta) (4-) complex: kinetics and mechanism
2005 (English)In: Journal of Molecular Liquids, ISSN 0167-7322, Vol. 118, no 1-3, 195-207 p.Article in journal (Refereed) Published
The [(CN)(5)Pt-T1(edta)](4-) complex, having direct metal-metal bond, has been prepared in solution by two different reactions: (a) dissolution of [(CN)(5)Pt-T1]((s)) in aqueous solution of edta ligand, (b) from Pt(CN)(4)(2-) and T1(edta)(CN)(2-) reactants. The decomposition reaction is greatly accelerated by cyanide and significantly inhibited by edta. It proceeds through the [(CN)(5)Pt-T1(CN)(3)](3-) intermediate. This complex decomposes to Pt(CN)(4)(2-) and T1(CN)(4)(-). To complete the reaction, T1CN)(4)(-) and edta(4-) react in relatively fast equilibrium step(s) giving T1(edta)(CN)(2-). The formation of [(CN)(5)Pt-T1(edta)](4-) complex can proceed via two different pathways depending on the ratio of the cyanide and the edta ligand. The 'direct path' at excess of edta means the formation of a [(CN)(4)Pt...T1(CN)(edta)](4-) intermediate followed by the release of the cyanide from the T1-center than the coordination of a cyanide from the bulk to the Pt-center of the intermediate. The 'indirect path' dominates in the absence of extra edta and the formation of the Pt-T1 bond happens between Pt(CN)(4)(2-) and T1(CN)(4)(-) as studied earlier in our laboratories.
Place, publisher, year, edition, pages
2005. Vol. 118, no 1-3, 195-207 p.
metal-metal bond, platinum, thallium, kinetics, mechanism, decomposition, cyano-complexes, edta, metal-metal bond, aqueous-solution, multinuclear nmr, constants, dissociation, equilibria, cyanide, c-13
IdentifiersURN: urn:nbn:se:kth:diva-14595DOI: 10.1016/j.molliq.2004.07.037ISI: 000227587900027ScopusID: 2-s2.0-13844272498OAI: oai:DiVA.org:kth-14595DiVA: diva2:332636
QC 20100525 QC 201110112010-08-052010-08-052011-10-11Bibliographically approved