Characterization and oxidative addition reactions of different rhodium and iridium triazolato complexes
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.
| Main Authors: | , , , , |
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| Format: | Digital revista |
| Language: | English |
| Published: |
The South African Chemical Institute
2010
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| Online Access: | http://www.scielo.org.za/scielo.php?script=sci_arttext&pid=S0379-43502010000100003 |
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| Summary: | 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. |
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