Uncovering the Mechanistic Scenarios of Nucleophilic Couplings in Cp*Co Systems

Identifier:  TDX:4679

Handle: https://hdl.handle.net/20.500.11797/TDX4679

Authors:  López Resano, Sara

Abstract:
The development of efficient synthetic methodologies for the construction of complex molecules has been a prominent area of research in recent decades. Ligand-directed transition metal-catalyzed C-H functionalization reactions have made significant strides in this regard, initially relying on noble transition metals. However, the emergence of more cost-effective first-row metals, such as cobalt, has provided an attractive and more sustainable alternative. Notably, Cp*Co(III) complexes have demonstrated their remarkable potential especially involving electrophiles as coupling partners, while methodologies involving nucleophiles remain scarce. This thesis advances the understanding of the participation of Cp*Co-based complexes in relevant nucleophilic couplings to form C–C and C–X bond-forming reactions. Specifically, we have explored: i) the mechanistic intricacies underlying C–SCF3 bond formation; ii) the mechanism of action of F+ oxidants leading to C–I bond formation; iii) nucleophilic coupling with a diverse family of well-established and isolable CpCo(III) complexes. By employing a combination of experimental and computational approaches, this thesis provides fundamental insights into the behavior of these complexes, including the unprecedented involvement of high-valent cobalt species in the targeted C-X reductive elimination events. The acquired knowledge not only enhances our understanding of the studied processes but also contributes to the broader field of knowledge-driven research in Chemistry.