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Title: Synthesis, characterisation and reactivity studies of novel strained [n]carbametallocenophanes (n = 2,3) containing cobalt and nickel
Author: Baljak, Sladjana
Awarding Body: University of Bristol
Current Institution: University of Bristol
Date of Award: 2013
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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.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available