Advancing main-group-metal mediation in synthesis and catalysis

Rights statement
Awarding institution
  • University of Strathclyde
Date of award
  • 2022
Thesis identifier
  • T16207
Person Identifier (Local)
  • 201869759
Qualification Level
Qualification Name
Department, School or Faculty
  • As described in the Impact Statement, the current worldwide efforts to improve sustainability is impacting almost every aspect of general life. In this regard, the chemical world is no different and a significant amount of research is being carried out in almost every area of chemistry to try and improve the sustainability and so-called “green-ness” of existing industrial processes. The work detailed within this thesis has been conducted with the goal of sustainability in mind, using main-group metal chemistry, with particular focus on the group 1 elements (especially sodium) for homogeneous catalysis. Reported herein is the synthesis and X-ray crystallographic characterisation of 23 new main-group metal compounds and demonstrations of their synthetic utility through their high (and often superior) reactivity. This spans metal alkoxide chemistry, hydroboration catalysis, hydrophosphination catalysis, and metal hydride chemistry. Heterobimetallic main-group metal species have also been explored, particularly alkali-metal aluminate compounds, with their special reactivity arising from the cooperativity between two different metals within the one co-complex. Alkoxide co-complexes 1 – 6 demonstrate rare examples of heavier (Na, K) alkali-metal alkoxy-aluminates and have shown themselves to be catalytically-active in the hydroboration of benzaldehyde. Sodium phosphide compounds 11 – 14 have shown excellent potency as catalysts for the hydrophosphination of alkenes and alkynes, with 13 and 14 in particular surpassing the performance of a considerable number of existing catalysts for this purpose, spanning every region of the periodic table. Finally, sodium aluminium hydride compounds 20 – 22 have shown the required potential to be synthetically-useful, with further work and examination, by providing the unexpected sodium tetraimino-dihydrido aluminate 23 when an addition reaction was attempted. All results discussed in this work underline the exciting developments currently happening in the area of main-group metal mediation and will no doubt provide a good platform for further investigation and impactful progress to be made.
Advisor / supervisor
  • Mulvey, Robert
Resource Type
Embargo Note
  • This thesis is restricted to Strathclyde users only until 1st May 2027.