The synthesis and characterisation of novel [2]dicarbacobaltocenophanes is described and their thermal reactivity studied, which led to unexpected reactivity, including C-C bond cleavage, disproportion and dimerisation. Additionally, chiral polyelectolytes were obtained, when the poly(cobaltocenoethylene) (PCE) was oxidised in the presence of chiral amino-acid based surfactants. The synthesised oligopolycobaltocene, which was formed by the ring-opening polymerisation (ROP) also exhibited chiral propel1ies in the oxidised state when chiral surfactants were chosen as counter anions. The first strained [3 ]tricarbanickelocenophane, with a flexible hydrocarbon-bridge was obtained via the 'fly-trap' method. Its detailed charactelisation is reported. Moreover, the reactivity of the [3]tricarbanickelocenophane towards NHCs as well as P- and N-donor ligands was studied . High-molecular weight cyclic polymers were obtained from the reaction of [3]tricarbanickelocenophane in pyridine, while the reaclion of the monomer and NaCp in different ratios afforded both cyclic and linear oligomers, respectively. Additionally, a cross-linked nickel-containing polymer was formed when the [3]tricarbanickelocenphane was heated to 80 DC in the absence of solvent. The pyrolysis of this material afforded magnetic ceramics, which were subject to fUl1her study . Furthermore the thermal reactivity of the cyclohexylsubstituted [2]dicarba ferrocenophane and the potential photolytic initiated ROP of [1 ]stalU1aferrocenophane have been explored.
Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:627974 |
Date | January 2013 |
Creators | Baljak, Sladjana |
Publisher | University of Bristol |
Source Sets | Ethos UK |
Detected Language | English |
Type | Electronic Thesis or Dissertation |
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