Trapping Elusive Cp*Co(III) Metallacycles: Implications in C-H Functionalization Processes

Identifier:  TDX:3344

Handle: https://hdl.handle.net/20.500.11797/TDX3344

Authors:  San Jose Orduna, Jesus

Abstract:
The conversion of ubiquitous and typically inert C–H bonds into C–C and C–heteroatom bonds is one of the most attractive transformation in organic chemistry. Among the different strategies developed over the past decades, ligand-directed transition-metal-catalyzed transformations have achieved remarkable progress, becoming an attractive alternative to traditional cross-coupling reactions. During decades, these catalytic systems required noble transition metals for the efficient construction of organic molecules. However, in the past few years, more cost-effective first-row metals, such as cobalt, have emerged as an appealing alternative to precious metals. In this context, the employment of Cp*CoIII complexes have represented a tremendous advance in cobalt catalysis, since they have the potential to promote a wide variety of C–C and C–heteroatom bond-forming reactions, via putative cyclometalated cobalt(III) species. Despite this significant progress, these cobalt systems are still at their infancy compared to Rh- or Pd-based ones, essentially due to the limited fundamental organometallic understanding of these systems. The investigation of the underlying reaction mechanisms of these transformations has been hampered by the difficulty to detect/isolate key intermediates. Challenged by the lack of fundamental knowledge of these transformations, in this Doctoral thesis we explore: i) the design and development of novel synthetic routes for accessing well-defined and stable cobalt metallacycles, analogous to proposed key reactive intermediates; ii) the employment of these Cp*CoIII metallacycles not only for unravelling previous inaccessible mechanistic intricacies of selected Cp*CoIII-catalyzed processes but also for improving their efficiency; and finally, iii) the participation and/or effect of some additives in different benchmark transformations. The fundamental knowledge generated during this Doctoral Thesis has led to important breakthroughs in cobalt catalysis, specially at molecular level.