Electrochemical and catalytic routes to small-molecule activation

Shipman, Michael A. (2020) Electrochemical and catalytic routes to small-molecule activation. PhD thesis, University of Glasgow.

Abstract

The work in this thesis is organised into five chapters:

In chapter 1 we discuss the importance of Ammonia and the various methods of synthesising it, with an emphasis on electrochemistry. During this introduction we will discuss the current and historical advances being made in the field, and comparing the various methods being employed to synthesise ammonia.

Chapter 2 is information about the various techniques and equipment used throughout the thesis. This should contextualise the methods used, so that the reader can understand why they have been employed.

Chapter 3 is the first research chapter, investigating the previously reported ability of Sn (II) Phthalocyanine complexes to reduce dinitrogen to ammonia. It was determined that there is no evidence for any catalysis in cyclic voltammetry or bulk electrolysis, and that any observed ammonia generation is either from contaminated Sn (II) Phthalocyanine, or due to electro-decomposition of these complexes under cathodic bias

In chapter 4, we investigate if stereoselective electrosynthesis is possible, in the context of the molecule 2,5-diacetoxy-2,5-dihydrofuran. We determined that in comparison to chemical methods prefer the cis isomer (2:1 cis:trans) as the major product, whereas the electrochemical synthesis prefers the trans product (7:5 cis:trans). In the course of this investigation, we solve the 3D crystal structure for 2,5-diacetoxy-2,5-dihydrofuran for the first time, as well as determined that it is possible to electrochemically synthesise 2,5- dibutoxy-2,5-dihydrofuran.

The 6th and final chapter is concerned with supramolecular coordination complexes (cages) and their ability to conduct host-guest reactions. We focused on small aromatic aldehydes and the Fe4L6 Nitschke cage. During our investigations we have shown that the cage molecule does indeed activate the carbonyl carbon for reaction with a weak hydride source. While the yields varied quite drastically, we have determined that smaller aldehydes (i.e. ones with less steric bulk) and ones with electronegative groups convert to the highest extent.

• Item Type: Thesis (PhD)
• Qualification Level: Doctoral
• Keywords: Electrochemistry, catalysis, host-guest chemistry, electrosynthesis, electrocatalysis, stereoselectivity, supramolecular chemistry, ammonia.
• Subjects: Q Science > QD Chemistry
• Colleges/Schools: College of Science and Engineering > School of Chemistry
• Supervisor's Name: Symes, Dr. Mark D.
• Date of Award: 12 February 2020
• Depositing User: Dr Michael A. Shipman
• Unique ID: glathesis:2020-79018
• Copyright: Copyright of this thesis is held by the author.
• Date Deposited: 10 Jun 2020 07:09
• Last Modified: 27 Jul 2023 10:25
• URI: https://theses.gla.ac.uk/id/eprint/79018

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