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Characterization and Oxidative Addition Reactions of Different Rhodium and Iridium Triazolato Complexes


AJ Muller
J Conradie
W Purcell
SS Basson
JA Venter

Abstract

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 1HNMR 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) × 10–2 L mol–1 s–1 in dichloromethane compared with 9.2(5) × 10–4 L mol–1 s–1 in benzene for iridium bpt-NH). 1HNMRdata 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.

Keywords: Rhodium(I), Iridium(I), Triazole, Cyclooctadiene, Oxidative Addition, Methyl Iodide, DFT

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eISSN: 1996-840X
print ISSN: 0379-4350