Design and synthesis of rhodium and iridium bis-η2 diolefin catalysts: : Applications in C–C bond formation and asymmetric catalysis

Abstract: This thesis deals with the design and synthesis of rhodium and iridium bis-η2 diolefin catalysts and their applications in C–C bond formation and asymmetric catalysis.More specifically, the second chapter describes the development of inter- and intramolecular (5+2) cycloadditions catalyzed by cationic iridium(I) complexes that lead to the formation of seven-membered rings in a single step. DFT was applied to investigate the mechanism of this reaction. Based on the findings described in Chapter 2, Chapter 3 discusses the relationship between the structure and the reactivity of a set of iridium and rhodium based bis–η2 diolefin complexes with respect to their application in four selected reactions.Chapters 4-6 discuss the design and development of chiral bis–η2 diolefin ligands and their application in asymmetric catalysis. The knowledge gained from the first chapters is applied to the development of C2-symmetric bis–η2 diolefin ligands and their complexation to transition metals. More specifically, Chapters 4 and 6 focus on the design, synthesis, and resolution of such chiral complexes, while their application and reactivity are discussed in chapter 5 and partly in chapter 6.