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Title: Synthesis and reactivity of superelectrophilic amidine disalts
Author: Scullion, Callum
ISNI:       0000 0004 5347 5835
Awarding Body: University of Strathclyde
Current Institution: University of Strathclyde
Date of Award: 2014
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This work describes the successful synthesis and full characterization of amidine disalt 4.1, which was made from the reaction of a tertiary amide with triflic anhydride and an amine; this disalt contains a dication which can be considered as a superelectrophile. Various related disalts (not limited to, but including disalts 3.43, 5.1 and 6.13) have also been synthesised and their reactivities further investigated. Chapter 1 gives an introduction to the concept of superelectrophiles, including the original discoveries in this area of chemistry. Chapter 2 focuses on reviewing the chemistry of [Fe]-hydrogenase, which converts amidine molecule 2.1 into diamino methylene 2.2; the possibility of a mechanism involving superelectrophiles is briefly highlighted. Chapter 3 reviews the previous work carried out within the Murphy group regarding superelectrophiles, leading on to the synthesis of disalt 3.43. Chapter 4 discusses the route to synthesising and isolating disalt 4.1. Additionally, Chapter 4 describes attempts at carrying out [Fe]-hydrogenase-related reactivity with disalt 3.43 and also describes the limitations of this disalt due to side-reactivity. The reasoning behind the synthesis of disalt 5.1 is discussed in Chapter 5; this chapter also discusses the successful reduction of this disalt with an iron hydride in a reversible process - the first successful model reaction of amidine disalts and iron hydrides, intended to mimic the possible reactivity within [Fe]-hydrogenase. Chapter 6 discusses non-hydrogenase reactivity of amidine disalts; evidence for the formation of monocationic carbene 6.1, the synthesis and reactivity of further substituted disalt 6.13 and the possibility of oxygen-containing disalts of type 6.56 are all discussed.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral