Self-assembly and bioinorganic chemistry of optically pure helical complexes
Howson, Suzanne E. (2011) Self-assembly and bioinorganic chemistry of optically pure helical complexes. PhD thesis, University of Warwick.Full text not available from this repository.
Official URL: http://webcat.warwick.ac.uk/record=b2491798~S15
Chapter 1 introduces the concept of helicates and the importance of chirality in these complexes. The different literature methods used to synthesise optically pure helicates are reviewed and their advantages and disadvantages discussed. Finally, a new approach towards synthesising diastereomerically pure helicatelike complexes is considered. Chapter 2 describes the syntheses of optically and diastereomerically pure factris( diimine) monometallic complexes of Fe(II) with d.r. > 200:1. The origins of this unprecedented stereo- and chemical selectivity are investigated via computational and structural studies, and compared with analogous complexes of other 3d metals (ZnII, CoII, CoIII). The reactivity of the optically and stereochemically pure Fe(II) complexes towards e.g. copper(I)-catalysed Huisgen 1,3-dipolar cycloaddition ‘click’ reactions is investigated. Recently published Cu(II) complexes of the same ligand by Min et al. are also discussed. Chapter 3 focuses on extending the chemistry described in Chapter 2 to design ligands capable of forming helicate-like structures. The resulting Fe(II) and Zn(II) bimetallic triple stranded complexes are diastereomerically pure with d.r. > 200:1. A detailed structural study is described based on a single crystal X-ray structure. The ability to add substituents to the pyridine rings successfully allows useful functionalities to be incorporated on the periphery of the structure. Chapter 4 describes the synthesis of a second family of diastereomerically pure helicate-like complexes. Useful functionalities are easily incorporated on the periphery of the structure via the use of different (R)-2-phenylglycinol derived amines in a one-pot synthesis. The reactivity of the alkyne hexa-functionalised Fe(II) complex towards copper(I)-catalysed Huisgen 1,3-dipolar cycloaddition reactions is also investigated. Chapter 5 focuses on the synthesis and biological applications of water soluble helicate-like bimetallic complexes. Specifically, experiments probing the binding of these complexes to DNA and DNA structural motifs are described. The antimicrobial activity of the complexes against the Gram-negative bacterium E. coli and the Gram-positive bacterium S. aureus (MRSA252) is also investigated. Chapter 6 details the experimental procedures used to carry out the work in this thesis.
|Item Type:||Thesis or Dissertation (PhD)|
|Subjects:||Q Science > QD Chemistry|
|Library of Congress Subject Headings (LCSH):||Complex compounds, Bioinorganic chemistry, Self-assembly (Chemistry)|
|Institution:||University of Warwick|
|Theses Department:||Department of Chemistry|
|Supervisor(s)/Advisor:||Scott, Peter, 1965 Dec. 10-|
|Sponsors:||Engineering and Physical Sciences Research Council (EPSRC)|
|Extent:||xxii, 236 leaves : ill., charts|
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