Periodic Reporting for period 2 - MUSYCA (MUltimetallic SYstems for C-H Activation processes)
Período documentado: 2021-08-01 hasta 2022-07-31
In our case, we need to speed up this process by making molecular models of these proteins in the laboratory. Through chemical synthesis, we can mimic the active sites of these enzymes by making analogues of the amino acid chains that hold the metals close together in the active site. These analogues are called ‘ligands’, and they are usually organic fragments that can be made in the lab in a short number of synthetic steps from commercially available reagents. The combination of rational ligand design and chemical synthetic methods is a powerful strategy to achieve this goal, since chemical modification of the ligands has a dramatic impact on the structure/activity relationship of the resulting bimetallic complexes.
Related to CH4 transformation, catalytic C-H activation is one of the most active areas of chemistry nowadays, given that selective functionalization of C-H bonds gives rise to a wide range of products that we use in our everyday lives. Particularly, C-H borylation (transformation of a C-H bond into a C-B bond) is an instrumental process in fields like carbohydrate analysis, novel materials or therapeutic agents, to name a few. In the latter case, the ability to selectively fuse organoboron species with other organic fragments via cross-coupling reactions is one of the main strategies employed in the pharmacological industry for the synthesis of new drugs. The utilization of copper-based catalysts in borylation reactions is an attractive methodology due to the low cost of the metal and the generally mild conditions required for these reactions to take place. In these processes, copper(I) boryl species have been invoked as reactive intermediates, but they are extremely challenging to isolate and study (they tend to decompose in solution releasing elemental copper). If we could synthesize, stabilize and isolate these compounds, we would be able to understand and modulate their properties so that we can design catalysts with better properties in terms of activity and/or selectivity.
In this project, the utilization of dinucleating 1,8-naphthyridine-based ligands has allowed us to synthesize a series of dicopper complexes, among which we can find dicopper(I) mu-boryl complexes which exhibit remarkable thermal stability (see next section). Additionally, structural models of some of the previously mentioned enzymes have been succesfully achieved with the synthesis of iron-containing homo- and heterobimetallic complexes stabilized by naphthyridine-based scaffolds.
The results obtained from this project have been disseminated in the form of scientific papers (Chem. Sci. 2022), national (XIIIth International School on Organometallic Chemistry Marcial Moreno Mañas, Spain) and international (29th International Conference on Organometallic Chemistry, Czech Republic) conferences.