FAculty of SCience
School of Cheistry
9910913j
messai@auvum.chem.wits.ac.za / The monodentate phosphine complexes bui3PMX (2a: M = Cu, X = Cl, 2b: M = Cu, X = I, 2c: M = Ag, X = Cl, 2d: M = Au, X = Cl) were synthesised in high yields from bui3P and MX. Their reaction with [Li{μ-N(R)C(but)C(H)R}]2 (R = SiMe3) gave the monomeric complexes bui3PCuN(R)C(but)=C(H)R (3a) and bui3PMC(H)RC(but)=NR (3b: M = Ag, 3c: M = Au) in moderate to high yields. The bonding mode in the 1-aza-allyl complexes 3a-c was found to depend strongly on the metal ion, with 3a being an enamide complex and 3b and 3c iminoalkyl complexes.
The reaction of bidentate ligand dpmaaH2 (2,3-bis(diphenylphosphino)maleic acid) with R2Sn-precursors led to novel dialkyl tin dpmaa complexes (R2Sn)(O,O dpmaa) (6) (where 6a, R = Me; 6b, R = Bu) were synthesized.
Complexation of the tin/phosphine complexes led to the heterobimetallic complexes {Au[(dpmaaO,O)(SnR2)]2}Cl (7a and 8a) {Au[(dpmaaO,O)(SnR2)][dpmaaH2]}Cl (7b and 8b) (where 7a and 8a, R = Me; 7b and 8b, R = Bu) and the mixed metal complexes {Au[(dpmaaO,O)(RuCl)]2}Cl (9a) {Au[(dpmaaO,O)(SnBu2)(dpmaaO,O)RuCl)]}Cl (9b) and {Au[(dpmaaO,O)(RuCl)][dpmaa]}Cl (9c).
All compounds were fully characterised by multinuclear NMR spectroscopy and microanalysis (not 3a, 3b, 4 and 5) solid state IR spectroscopy (KBr-pellets) (4-9) and mass spectrometry (6-8). The solid state structures of complexes 2c, 2d, 3c, 6a and 6b (two polymorphs) have been determined by X-ray crystallography revealing the presence of rare trimeric macrocycles in the case of 6a and 6b.
The anti-tumour activity of the metal complexes (6b and 7-9) was tested on a single cell-line (except 7a and 8a which were on eight cell-lines) and their activity was compared to cisplatin.
| Identifer | oai:union.ndltd.org:netd.ac.za/oai:union.ndltd.org:wits/oai:wiredspace.wits.ac.za:10539/1648 |
| Date | 13 November 2006 |
| Creators | Mamo, Messai Adenew. |
| Source Sets | South African National ETD Portal |
| Language | English |
| Detected Language | English |
| Type | Thesis |
| Format | 84789 bytes, 1775324 bytes, application/pdf, application/pdf, application/pdf, application/pdf |
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