Acronym : OVATION
Project leader : F. Palmino
Partnership : Paris Chemistry Research Institute and FEMTO-ST
Abstract :
Activation of small molecules, such as N2 by metal-based complexes often occurs via mechanisms involving changes in redox state, spin state, bond breaking and formation. Therefore radical reactions are particularly suited for providing insights into such aspects. In order to control radical reactions and to observe directly (side) reactions, on-surface synthesis can have a central role in radical chemistry. Clearly, such research topic requires a concerted and global approach, including synthetic skills for complex design and synthesis, an in-depth understanding of mechanistic and kinetic aspects of the interaction of small molecules with the activating entity, and explanatory as well as predictive support from theoretical expertise. In this regard, both partners initiated their first collaboration in 2016 to exploit the synthetic possibilities of free radicals’ high reactivity for the development of a new tandem synthetic method. We performed controlled excitations of molecules by using inelastic-electron-tunnelling induced manipulation processes. As a result of our work, it is now possible to form tip-induced radicals that are able to cross-react in a controlled manner to produce alkyl oligomers. OVATION aims to take advantage of these new links and this concerted and collaborative approach to resolve important open questions in the chemistry of small molecules, such as: What conditions and perturbation is needed to move an inert molecule such as N2 out of its comfort zone to become a reagent? What concept and what strategy is required to induce the appropriate configuration on the metal centre to bind such small molecules, and eventually to perturb their ground state to such an extent that a reaction starts to occur, ideally in a catalytic manner? Although this is an ambitious and challenging objective, previous results from both partners in controlling an electron-triggered tandem reaction already confirm the feasibility and scientific correctness of this approach. OVATION combines the expertise of two world leaders in surface science and organometallic chemistry/catalysis, precisely with the goal of examining this interdisciplinary research field in detail. This research is cross-cutting, and combines for the first-time researchers studying on-surface radical catalysis, using complementary techniques from both domains of research to develop a unique strategy of activation of small molecules.
Nature of the projet : recherche
Funding agency : ANR
Grant or funding obtained : 350 k€
Project strat and end date : 02/2020 – 02/2024