Novel Group 3/Lanthanide complexes and their application to intramolecular hydroamination and ring-opening polymerisation

This thesis describes the synthesis, characterisation and reactivity studies of a range of Group 3/Lanthanide complexes supported by bis(oxazolinyl)phenyl amide (BOPA). Chapter 1: Provides an introduction to the properties of the Lanthanides. Their application in asymmetric catalysis is reviewed, including catalysts supported by oxazoline ligands. Chapter 2 Describes density functional theory on a series of Group 3 BOPA complexes, the synthesis and characterisation of a new scandium amide-chloride precursor, thirty Group 3/lanthanide compounds supported by BOPA, six cation compounds supported by BOPA and three lithium BOPA compounds along with a discussion of the reactivity of compounds. Chapter 3: Describes the application of compounds described in Chapter 2 to the intermolecular hydroamination reaction of aminoolefins. Chapter 4: Describes a brief introduction to ring-opening polymerisation of rac-lactide and the application of compounds described in Chapter 2 to the ring-opening polymerisation of rac-lactide. Chapter 5: A brief introduction to luminescence is provided and the photophysical properties of a selection of diamagnetic complexes and all paramagnetic complexes discussed in Chapters 2 are described. Also, the synthesis, characterisation and photophysical properties of five Group 3/lanthanide compounds supported by pseudosubstrate ligands are described. Chapter 6: Details full experimental procedures and contains characterising data for all new compounds. Appendices A-B: Full tables of crystallographic data for all new crystallographically characterised compounds described herein are provided in Appendix A. Publications from this thesis are provided in Appendix B