[n]Metallocenophanes and polymetallocenes of iron, cobalt and nickel : synthesis, reactivity, properties and applications

• Main Author: Musgrave, Rebecca Alice
• Published: University of Bristol 2016
• Subjects: 547
• Online Access: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.702753

This thesis describes several projects based on the synthesis, characterisation and reactivity of [n]metallocenophanes of iron, cobalt and nickel, and the properties and applications of the related polymetallocenes. Chapter 2 describes the synthesis of sila[l]ferrocenophanes bearing bulky substituents and the polymerisation of these monomers by thermal and photolytic ROP. Discussion focuses on the influence of steric bulk on the polymerisation mechanisms, and characterisation of polymer tacticity by NMR spectroscopy. Chapter 3 details the reversible ROP of tricarba[3]nickelocenophane and the evaluation of thermodynamic parameters for the polymerisation. The ROP of various other [n]nickelocenophanes and their propensity toward ring-opening is also described. Chapter 4 details the electrochemical investigation of [n]nickelocenophanes and poly(nickelocenylpropylene), and the chemical oxidation of these species. Reactivity of [n]nickelocenophanes with donor molecules 2,2'-bipyridine and an N-heterocyclic carbeneis also discussed. Chapter 5 encompasses three separate projects: the synthesis of novel cobaltocene-containing molecules, the synthesis and self-assembly of poly(cobaltoceniumethylene) chiral surfactant complexes, and the application of poly( cobaltoceniumethylene) materials in the protection of β-lactam antibiotics. Chapter 6 describes the abstraction of hydride from an amino-substituted sila[l]ferrocenophane and the dimerisation of the silyl cation-containing product, in addition to the ring-opening reactivity of dimethylsila[ 1 ]ferrocenophane with chloro(trimethylphosphine )gold. Chapter 7 presents ongoing projects and potential avenues for future work, based on the results detailed in Chapters 2-6.