SciELO - Scientific Electronic Library Online

vol.64Characterization of South African coal for metals, inorganic and organic sulfur compoundsTwenty golden years of battery R&D at CSIR, 1974-1994 author indexsubject indexarticles search
Home Pagealphabetic serial listing  

Services on Demand



Related links

  • On index processCited by Google
  • On index processSimilars in Google


South African Journal of Chemistry

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


CONRADIE, Jeanet. Structure of coordination complexes: The synergy between NMR spectroscopy and computational chemistry. S.Afr.j.chem. (Online) [online]. 2011, vol.64, pp.190-202. ISSN 1996-840X.

Illustrative examples of how NMR spectroscopy and computational chemistry data can be used in synergy to gain information on structure, coordination mode, bonding, symmetry and isomeric distribution of transition metal complexes, is presented. Isomer distribution and the most stable structures in a series of Ti(/3-diketonato)2Cl2 and Ti(β-diketonato)2(biphen) complexes as determined by density functional theory (DFT) methods and the application of the Boltzmann equation, are in agreement with crystal structures and variable temperature NMR results. Secondly, the DFT determined coordination mode of the 4-amino-3,5-bis(pyridine-2-yl)-1,2,4-triazole, (bpt-NH2) which has the appropriate chemical geometry to behave as anionic or neutral bidentate chelating group to form a 5- or 6-membered complex, is shown to be in agreement with 1Ή NMR shifts for [Rh(bpy)2(bpt-NH)]2+, [Rh(phen)2(bpt-NH)]2+, [Rh(bpt-NH)(cod)] and [Ir(bpt-NH)(cod)] (cod = 1,5-cyclooctadiene, phen = 1,10-phenanthroline, bpy = 2,2'-bipyridine). The oxidative addition of CH3I to [Rh(/3-diketonato)(CO)(PPh3)] complexes consist of three reaction steps and involves isomers of two different RhIII-alkyl and two different RhIII-acyl species. For this reaction experimental 1Ή NMR techniques complement the stereochemistry of reaction intermediates and products as calculated by density functional theory. NMR properties, in agreement with computational results, proved to be useful to access the nature of the κ3 to κ2 distortion in coinage metal-ethylene complexes supported by tris(pyrazolyl)borates. The last example showed that NMR, X-ray crystal and computational results showed C2 symmetry for a series of metal(II) complexes coordinated to a 16-membered pentaaza macrocycle.

Keywords : DFT; computational; organometallic; NMR spectroscopy.

        · text in English     · English ( pdf )


Creative Commons License All the contents of this journal, except where otherwise noted, is licensed under a Creative Commons Attribution License