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South African Journal of Chemistry

On-line version ISSN 1996-840X
Print version ISSN 0379-4350

S.Afr.j.chem. (Online) vol.63  Durban  2010

 

RESEARCH ARTICLE

 

Characterization and oxidative addition reactions of different rhodium and iridium triazolato complexes

 

 

Alfred J. Muller; Jeanet Conradie*; Walter Purcell*; Stephen S. Basson; Johan A. Venter

Department of Chemistry, University of the Free State, Bloemfontein 9300, South Africa

 

 


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 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.

Keywords: Rhodium(I), iridium(I), triazole, cyclooctadiene, oxidative addition, methyl iodide, DFT


 

 

Full text available only in PDF format.

 

Acknowledgements

Financial assistance by the South African National Research Foundation and the Central Research Fund of the University of the Free State is gratefully acknowledged.

 

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Received 17 June 2009
Revised 7 December 2009
Accepted 20 January 2010

 

 

* To whom correspondence should be addressed. E-mail addresses: purcellw@ufs.ac.za / conradj@ufs.ac.za.

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