Thesis
Understanding & exploiting selectivity in nickel-catalysed cross-coupling
- Creator
- Rights statement
- Awarding institution
- University of Strathclyde
- Date of award
- 2020
- Thesis identifier
- T15886
- Person Identifier (Local)
- 201689947
- Qualification Level
- Qualification Name
- Department, School or Faculty
- Abstract
- This project was focused on investigating structure & reactivity relationships between nickel(0) species derived from nickel(II) sources and aryl halides with coordinating π systems in Suzuki cross-coupling reactions. Design of Experiments was used to optimise the cross-coupling conditions to achieve satisfactory conversions and robust reproducibility. Competition couplings were designed in order to compare the conversion of halides with and without coordinating functional groups, as well as between electron rich and poor systems to decouple any selectivity effect from the electronic effects. The selectivity in favour of coordinating substrates was quite prominent with several of the halides. The selectivity that was observed was quantified and investigated with an analogous palladium(II) complex, where it was found that this effect was less pronounced. A robustness screen was also carried out to investigate any inhibition to coupling that these coordinating groups might exhibit. Calorimetry was employed in an attempt to glean kinetic information about the reaction and whether there were significant rate differences in the couplings of these halides. Finally, the investigation was extended towards heterocyclic aryl chlorides, where novel nickel(II) dimers were characterised by X-ray crystallography and found to inhibit the coupling of ortho-halo heteroarenes.
- Advisor / supervisor
- Nelson, David
- Resource Type
- DOI
- Date Created
- 2020
- Former identifier
- 9912990093402996
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