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Radiochemistry

, Volume 56, Issue 2, pp 156–161 | Cite as

Reactivity of Tc(I) tetracarbonyl complexes

  • G. V. SidorenkoEmail author
  • A. E. Miroslavov
  • D. A. Maltsev
  • A. A. Lumpov
  • Yu. S. Polotskii
  • M. Yu. Tyupina
  • D. N. Suglobov
Article

Abstract

Technetium tetracarbonyl complexes [TcBr(CO)4]2 and [TcXan(CO)4] (Xan is methylxanthate), being fairly stable in an inert solvent, undergo rapid decarbonylation in a donor solvent (acetonitrile). The kinetic characteristics of the reaction were determined. The experimental data and results of quantum-chemical calculations allow a conclusion that the reaction, as in the case of pentacarbonyl halides, occurs via dissociative pathway with a lower energy barrier as compared to pentacarbonyl halides. The results obtained were interpreted assuming the formation of unstable complexes of intermediate five-coordinate technetium species with an “inert” solvent molecule and the effect of this phenomenon on the relative stability of the technetium penta- and tetracarbonyl complexes. The technetium complex [TcXan(CO)4] is considerably less stable than its rhenium analog.

Keywords

technetium rhenium tetracarbonyl complexes acetonitrile xanthate decarbonylation kinetics quantum-chemical calculations 

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Copyright information

© Pleiades Publishing, Inc. 2014

Authors and Affiliations

  • G. V. Sidorenko
    • 1
    Email author
  • A. E. Miroslavov
    • 1
  • D. A. Maltsev
    • 2
  • A. A. Lumpov
    • 1
  • Yu. S. Polotskii
    • 1
  • M. Yu. Tyupina
    • 1
  • D. N. Suglobov
    • 1
  1. 1.Khlopin Radium InstituteSt. PetersburgRussia
  2. 2.Chemical FacultySt. Petersburg State UniversitySt. PetersburgRussia

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