This thesis reports a study of polydentate amino acid complexes of cobalt(III). The complexes prepared during this project have been characterized by a range of techniques, including ¹³C{¹H} and ¹H NMR spectroscopy, UV-visible spectroscopy, infra-red spectroscopy, elemental analysis and single crystal X-ray structure determination. A total of seven single crystal X-ray structure determinations have been performed during these studies. The imino acid polydentate complex, [Co(Aim₂trien)]₂[ZnCl₄], was reduced to the corresponding amino acid complex, [Co(A₂trien)]Cl, where as many as ten diastereoisomers could be formed due to the formation of new stereogenic centres. The crude product of these reactions was a mixture of isomers, according to ¹³C{¹H} NMR data. These isomers were separated using ion-exchange chromatography. The major isomer (I1), a minor isomer (I2a) and a half reduced complex (I4a) from the [Co(A₂trien)]Cl reduction and separation experiment were characterised. The predominant isomers produced were found to have had the proton on the α-carbon atoms positioned on the amine face of each amino acid ligand fragment. To investigate the ratio of the isomers formed by the initial borohydride reduction, an isomerisation study of the major isomer of the [Co(A₂trien)]⁺ complex (I1) was performed. This study hoped to establish the degree to which the distribution of isomers was a result of dynamic equilibrium. Experiments on a small scale showed the initial isomer distribution to be similar to that obtained from the borohydride reduction reaction. However, prolonged exposure to the carbonate buffer (≈ two weeks) resulted in isomers not previously seen. Experiments on a large scale were performed to establish whether the results were consistent. The materials from both the two hour and two week experiments were mixtures of isomers by ¹³C{¹H} NMR spectroscopy and were separated using ion-exchange chromatography. ¹H NMR data of the two hour experiment showed only epimerisation of the amine proton adjacent to the α-carbon atom. Therefore the isomers produced from the isomerisation of I1 have the same configuration of the proton on the α-carbon atoms, which is on the amine face of each amino acid chelate ring. ¹H NMR data from the two week experiment resulted in new isomers not previously seen as both the amine proton and the proton on the α-carbon atom have been epimerised. The polyamine wrapping around the central metal ion may also have changed in some cases. It would appear, from the ¹H NMR data that the methyl group signals of these isomers fall in two distinct clusters; a cluster at δ 1.50-1.65 ppm and a cluster at δ 1.40-1.49 ppm. From these results, and the results of Chapter Two, it has been calculated that there is at least 92% facial selectivity for the amine face of the molecule during the initial borohydride reduction reactions. This may be due to a di-hydrogen bonding interaction between an adjacent amine proton and a hydride of the borohydride, which directs the attack. Following on from this study, a new range of imino and amino acid complexes were synthesised using different tetraamine and pentaamine cobalt(III) complexes. X-ray quality crystals of [Co(Aim₂2,2,3-tet)][ClO₄] and [Co(Aim₂2,3,2-tet)][ClO₄] were obtained and solved with assistance from Dr. Chris Fitchett and Dr. Jennifer Burgess. Borohydride reductions were performed on the [Co(Aim₂2,2,3-tet)]⁺ and [Co(Aim₂2,3,2-tet)]⁺ systems. The products were a mixture of isomers according to 1H and ¹³C{¹H} NMR spectroscopy. The results from the ¹H NMR experiments showed similarity between the [Co(A₂2,3,2-tet)]⁺ and [Co(A₂trien)]⁺ systems, where three major stereoisomers were present in solution. Analogous results for the asymmetric [Co(A₂2,2,3-tet)]⁺ system were also observed. Preliminary attempts have been made to separate these isomers using ion-exchange chromatography.
| Identifer | oai:union.ndltd.org:ADTP/274125 |
| Date | January 2009 |
| Creators | Wilson-Coutts, Sarah Mary |
| Publisher | University of Canterbury. Chemistry |
| Source Sets | Australiasian Digital Theses Program |
| Language | English |
| Detected Language | English |
| Rights | Copyright Sarah Mary Wilson-Coutts, http://library.canterbury.ac.nz/thesis/etheses_copyright.shtml |
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