Reactivity of Tc(I) tetracarbonyl complexes
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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.
Keywordstechnetium rhenium tetracarbonyl complexes acetonitrile xanthate decarbonylation kinetics quantum-chemical calculations
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- 1.Technetium, Rhenium and Other Metals in Chemistry and Nuclear Medicine, Mazzi, U., Ed., Padova: SGEditoriali, 2006, vol. 7.Google Scholar
- 2.Technetium and Other Radiometals in Chemistry and Medicine, Mazzi, U., Eckelman, W.C., and Volkert, W.A., Eds., Padova: SGEditoriali, 2010.Google Scholar
- 5.Miroslavov, A.E., Sidorenko, G.V., Borisova, I.V., et al., Radiokhimiya, 1990, vol. 32, no. 4, pp. 6–14.Google Scholar
- 6.Miroslavov, A.E., Sidorenko, G.V., Borisova, I.V., et al., Radiokhimiya, 1990, vol. 32, no. 6, pp. 14–21.Google Scholar
- 8.Borisova, I.V., Miroslavov, A.E., Sidorenko, G.V., and Suglobov, D.N., Radiokhimiya, 1991, vol. 33, no. 3, pp. 1–9.Google Scholar
- 9.Borisova, I.V., Miroslavov, A.E., Sidorenko, G.V., et al., Radiokhimiya, 1991, vol. 33, no. 4, pp. 27–38.Google Scholar
- 12.Baturin, N.A., Grigor’ev, M.S., Kryuchkov, S.V., et al., Radiokhimiya, 1994, vol. 36, no. 3, pp. 202–204.Google Scholar