This dissertation describes investigations into novel reactivity modes of strained [nJmetallocenophanes of the late transition metals. Chapter 1 introduces the topic of metallocenes, their structure and bonding and the incorporation of these species into strained [n metallocenophanes. Specific emphasis is placed on the various strain- and redox-induced reactivity modes of ansa metallocenes, including ROP to afford polymetallocenes. Selected examples of the utility of these metal- containing polymers in various applications are also presented. Chapter 2 describes investigations that deduce the mechanism of thermal ring-opening polymerisation (ROP) of dicarba[2Jferrocenophanes as a heterolytic Fe-Cp bond cleavage process. The elucidation of a structure-thermal reactivity relationship for thermally-induced bond cleavage processes of dicarba[2Jferrocenophanes is also discussed. Chapter 3 describes an extension of the studies presented in Chapter 2 to new molecular analogues of dicarba[2Jferrocenophanes and their associated oligo- and polymers. The elucidation of a carbon-carbon bond-cleavage pathway which proceeds in the absence of ring-strain is also detailed. Chapter 4 explores the redox-induced reactivity of [nJruthenocenophanes, including oxidative dirilerization, novel reactivity· modes at the metal centre and a yts _yt3 haptotropic Cp ring slippage with a cyclo-dimerization process. Chapter.S details the ROP of strained [nJnickelocenophanes to afford polynickelocenes, an interesting class of metallopolymers with an S = 1 monomer unit. Investigations of the redox properties of these species will also be presented. Chapter 6 describes the low temperature synthesis of mixed-metal alloy FePd nanoparticles from single-source heterobimetallic [l]ferrocenophane precursors. Analysis of the resulting particles will also be presented. Chapter 7 present: ongoing and potential future avenues of exploration inspired from the results presented within this dissertation.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:658199 |
| Date | January 2014 |
| Creators | Russell, Andrew |
| Publisher | University of Bristol |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
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