The decomposition and formation of the platinum-thallium bond in the [(CN)5Pt-Tl(edta)]4- complex: Kinetics and mechanism

Péter Nagy, Róbert Jószai, István Fábián, Imre Tóth, Julius Glaser

Research output: Contribution to journalConference article

4 Citations (Scopus)

Abstract

The [(CN)5Pt-Tl(edta)]4- complex, having direct metal-metal bond, has been prepared in solution by two different reactions: (a) dissolution of [(CN)5Pt-Tl](s) in aqueous solution of edta ligand, (b) from Pt(CN)42- and Tl(edta)(CN)2- reactants. The decomposition reaction is greatly accelerated by cyanide and significantly inhibited by edta. It proceeds through the [(CN) 5Pt-Tl(CN)3]3- intermediate. This complex decomposes to Pt(CN)42- and Tl(CN)4 -. To complete the reaction, Tl(CN)4- and edta4- react in relatively fast equilibrium step(s) giving Tl(edta)(CN)2-. The formation of [(CN)5Pt-Tl(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)4Pt...Tl(CN)(edta)]4- intermediate followed by the release of the cyanide from the Tl-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-Tl bond happens between Pt(CN)42- and Tl(CN) 4- as studied earlier in our laboratories.

Original languageEnglish
Pages (from-to)195-207
Number of pages13
JournalJournal of Molecular Liquids
Volume118
Issue number1-3
DOIs
Publication statusPublished - Apr 15 2005
EventContributions to the 28th International Conference on Solution Chemistry -
Duration: Aug 23 2003Aug 28 2003

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Keywords

  • Cyano-complexes
  • Decomposition
  • Edta
  • Kinetics
  • Mechanism
  • Metal-metal bond
  • Platinum
  • Thallium

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Spectroscopy
  • Physical and Theoretical Chemistry
  • Materials Chemistry

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