A series of five, tetradentate Schiff-base ligands were synthesised and chelated to vanadyl to form
oxovanadium(IV) complexes. The ligands, 4,4’-{benzene-1,2-diylbis[nitrilo(1E)phen-1-yl-1ylidene]}-
dibenzene-1,3-diol (H2L1), 4,4’-{ethane-1,2-diylbis[nitrilo(1E)phenyl-1-yl-1-ylidene]}dibenzene-1,3-diol
(H2L2), 4,4’-{propane-1,2-diylbis[nitrilo(1E)phen-1-yl-1-ylidene]}dibenzene-1,3-diol (H2L3), 4,4’-{(2-
hydroxypropane-1,3-diyl)bis[nitrilo(1E)phen-1-yl-1-ylidene]}dibenzene-1,3-diol (H2L4) and 4,4’-{2,2-
dimethylpropane-1,3-diyl)bis-[nitrilo(1E)phen-1-yl-1-ylidene]}-dibenzene-1,3-diol (H2L5), characterised by
TOF-MS, IR, electronic absorption, 1H and 13C NMR spectroscopy. The ligand H2L5 was also characterised
by XRD. The ligands were shown to have a bis-zwitterionic structure in the solid state, and possibly also in
solution. Complexes were characterised by Elemental Analysis, TOF-MS, IR, electronic absorption spectra,
EPR and 51V NMR spectroscopy. They form mononuclear complexes, with one ligand binding a single
vanadyl ion.
EPR spectroscopy was performed on both the powdered form and solutions of the complexes. All the
complexes displayed axial symmetry, with increasing distortion from an ideal square pyramidal geometry
as the size and bulk of the central chelate ring was increased. Isotropic g0 values suggest solvent
interaction with the vanadium ion for the coordinating solvent DMSO. Additional distortion on the
coordination geometry, presumably from the benzyl groups of the compounds, causes the isotropic
hyperfine coupling constants to be greater than expected.
Furthermore, the ability of the complexes to bind peroxide species was investigated by following the
addition of H2O2 to the complexes using 51V NMR spectroscopy to observe shielding changes at the
vanadium nucleus, and 1H NMR spectroscopy to monitor the bulk magnetic susceptibility, via a modified
Evan’s NMR method. Similar experiments were done with sodium hydroxide for comparison. As expected,
the oxoperoxovanadium(V) complexes were more stable than their progenitor oxovanadium(IV)
complexes. Additionally, increasing the distortion from the ideal pseudo square-pyramidal coordination
geometry for the vanadyl ion resulted in a greater increase in the apparent stability of the peroxocomplexes.
This latter effect is further enhanced by the addition of a hydrogen-bonding group in close
proximity to the vanadium nucleus.
DFT calculations of the optimized geometries, natural bond orbitals, electronic absorption and infra-red
frequencies were performed for both the ligands and the complexes; nuclear magnetic resonance
calculations were performed for the ligands as well. The B3LYP/6-311G (d,p) and B3LYP/LANL2DZ level of
theories were used for the ligands and complexes respectively, except for electronic transitions, which
were calculated using TD-SCF methods for both ligands and complexes. Calculated and experimental
results were compared where possible, and showed reasonable agreement for all calculations performed.
The exception to this was for the NMR calculations for the ligands, which were poorly simulated.
Finally, the in vitro biological activity of the complexes was evaluated for cytotoxicity against the human
tumour cell lines: A549, U251, TK-10 and HT29, via an MTT assay. All complexes showed promising
anticancer activity, as evidenced by their low IC50 values for the cell lines A549, U251 and TK-10, which are
in general, lower than that observed for cisplatin. They did, however, express negligible activity against
the HT29 colon adenocarcinoma cell line; showing an apparent selectivity for certain cell lines. These
oxovanadium(IV) complexes, thus warrant further evaluation as chemotherapeutic agents. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2012.
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:ukzn/oai:http://researchspace.ukzn.ac.za:10413/8894 |
| Date | January 2012 |
| Creators | Bartlett, Malcolm Alan. |
| Contributors | Munro, Orde Q., Akerman, Matthew P. |
| Source Sets | South African National ETD Portal |
| Language | en_ZA |
| Detected Language | English |
| Type | Thesis |
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