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Title: Catalytic dehydropolymerisation of amine- and phosphine-boranes as a route to structurally diverse materials
Author: Resendiz-Lara, Diego
ISNI:       0000 0004 7961 6763
Awarding Body: University of Bristol
Current Institution: University of Bristol
Date of Award: 2019
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This thesis describes the synthesis and characterisation of polyamino- and polyphosphinoboranes, targeting the use of catalytic dehydropolymerisation as a route to obtain polymers with varied structures. Chapter 1 puts into context of the area of metal-catalysed dehydrocoupling chemistry of main group compounds with an emphasis on amine- and phosphine-boranes as precursors to polymeric materials, and the properties and potential applications of the related inorganic polymers. Chapter 2 describes the synthesis of a family of aryl-substituted phosphine-boranes with electron-donating and electron-withdrawing groups and the polymerisation of these monomers by metal-catalysed dehydropolymerisation using [CpFe(CO)2OTf] as a precatalyst. The discussion focuses on the influences of the electronics of the substituents in the side chains on the properties of the polymers, and the study of their thermal properties, as well as their potential applications. Chapter 3 describes the expanded use of [CpFe(CO)2OTf] as a versatile precatalyst for the dehydropolymerisation of a range of alkyl-substituted phosphine-boranes with varied structures. Although preliminary investigation was hampered by monomer purity, the discussion focuses on the potential factors that could affected the monomer's reactivity. The thermal properties of poly(alkylphosphinoboranes) are also discussed. Chapter 4 presents the use of amine-boranes substituted by aryl-containing alkyl groups at nitrogen via catalytic dehydropolymerisatiom aided by transition metal precatalysts. The formation of high molar mass homopolymers and copolymers is described along with thermal stability and cross-linking studies. Discussion on the molar mass characterisation of polyaminoboranes by different analytical techniques is also described. Chapter 5 describes the unprecedented synthesis and characterisation of the BN inorganic analogues of polystyrene, poly(B-arylaminoboranes) through metal-catalysed dehydropolymerisation of B-substituted amine-boranes. In addition, the stability studies in the solid state and in solution for these polymers is presented. Chapter 6 presents ongoing and potential ideas for future work based upon the results presented in Chapter 2-5.
Supervisor: Manners, Ian Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available