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South African Journal of Chemistry

versão On-line ISSN 1996-840X

Resumo

MULLER, Alfred J. et al. Characterization and oxidative addition reactions of different rhodium and iridium triazolato complexes. S.Afr.j.chem. (Online) [online]. 2010, vol.63, pp. 11-19. ISSN 1996-840X.

A number of different rhodium(I) and iridium(I) triazolato complexes and their oxidative addition products (triazolate = 3,5-bis(pyridine-2-yl)-1,2,4-triazolate (bpt-) and 4-amino-3,5-bis(pyridine-2-yl)-1,2,4-triazolate (bpt-NH-)) were prepared and characterized by means of IR and 1H NMR spectroscopy, elemental analysis and computational chemistry methods. The oxidative addition reactions of these complexes with iodomethane in different solvents indicated simple second-order kinetics with the faster reactions in the more polar solvents (1.44(7) x 10-2 L mol-1 s-1 in dichloromethane compared with 9.2(5) x 10-4 L mol-1 s-1 in benzene for iridium bpt-NH). 1H NMR data and density functional theory calculations illustrate that the coordination of the metal centre in [M(bpt-NH)(cod)] (M = Rh or Ir) occurs via the amine moiety and a nitrogen of a pyridine ring.

Palavras-chave : Rhodium(I); iridium(I); triazole; cyclooctadiene; oxidative addition; methyl iodide; DFT.

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