Thesis

Computationally guided catalyst design towards enhanced iridium(I) catalysts

Creator
Rights statement
Awarding institution
  • University of Strathclyde
Date of award
  • 2024
Thesis identifier
  • T16972
Person Identifier (Local)
  • 201983896
Qualification Level
Qualification Name
Abstract
  • Over the past 50 years the area of C–H activation and functionalisation has grown profusely and the associated area of hydrogen isotope exchange (HIE), has seen significant advances. Our laboratories have developed a variety of monodentate iridium(I) catalysts which are capable of highly efficient HIE of a wide scope of substrates. In addition to these studies, the same laboratory has also developed a small array of bidentate iridium(I) catalysts which have enabled the labelling of substrates bearing more sterically encumbered directing groups. Utilising the information gained from these HIE studies, the application of a bidentate iridium(I) NHC-phosphine catalyst has been expanded towards the area of C-C bond formation. Specifically, this bidentate catalyst has been shown to catalyse the intramolecular hydroarylation of alkenes to produce dihydrobenzofuran scaffolds. The work presented within this thesis has successfully optimised this C-C bond forming hydroarylation process by employing a design of experiments (DoE) approach. Furthermore, the scope of this process has been expanded to encompass the hydroarylation of 17 substrates. From a computational perspective, DFT calculations have been employed to elucidate a potential reaction mechanism for this process in silico. Building upon this initial computational work, in silico parameterisation has been conducted to identify promising bidentate ligand scaffolds which have the potential to improve the C-C bond forming process. Ligand parameters, such as percent buried volume and the calculated Tolman electron parameter, were utilised to assess the steric and electronic properties of potential bidentate ligands. To date, no alternative ligand scaffolds have provided an improvement on the established ethylene-linked bidentate iridium(I) NHC-phosphine catalyst. Finally, the HIE process for the labelling of sterically encumbered aryl-carbamates has been investigated. More specifically, mechanistic investigations have been conducted in an attempt to determine a kinetic isotope effect for this process in various reaction vessels
Advisor / supervisor
  • Kerr, William J.
Resource Type
DOI
Embargo Note
  • The digital version of this thesis is restricted to Strathclyde users only until 7th June 2029.

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