Periodic Reporting for period 1 - CCIMC (Coordination chemistry inspires molecular catalysis)
Reporting period: 2020-03-01 to 2022-02-28
Catalysis is a key technology for Europe. The production of 80% of industrially relevant chemicals involves catalysis, which accounts for about 20-30% of World Gross Domestic Product. Therefore, catalysis lies at the heart of our chemical industry. Molecular catalysis is more efficient and selective than heterogeneous catalysis, while more robust and simpler to implement than the enzymatic approach used in biotechnologies. Major challenges for the future of mankind, where catalysis plays a determining role, are the development of “greener”, environmentally benign processes, the transition from fossil to renewable feedstocks for both energy and consumer products. Related issues are the mechanistic understanding of the catalytic processes, which is essential for optimization (greater productivity, lower energy consumption, lower waste production), and catalyst recovery (lower product contamination, preservation of low earth-abundant metal resources). Europe is a leading player in both academic catalysis research as well as its industrial implementation, but this leadership is increasingly challenged by emerging as well as mature but still innovating economies. The aim of this ITN is to palliate research fragmentation by coordinating an innovative research programme at the European scale, on the basis of double doctoral degrees with the direct involvement of industrial partners, to train the next generation of researchers in molecular catalysis. Fifteen Early Stage Researchers (ESRs) participate in the programme, each one working on a doctoral thesis jointly between two beneficiary research institutions in two different countries and with a secondment research period in one of the non-academic partner institutions.
The action is structured in eight separate work packages (WP). In addition to the project management (WP1), it comprises four interlinked scientific work packages (WP2, ligand design; WP3, precatalyst development; WP4, reactions and mechanisms; WP5 catalytic studies), a training work package (WP6), an outreach and public engagement work package (WP7) and an ethics work package (WP8).
The action is structured in eight separate work packages (WP). In addition to the project management (WP1), it comprises four interlinked scientific work packages (WP2, ligand design; WP3, precatalyst development; WP4, reactions and mechanisms; WP5 catalytic studies), a training work package (WP6), an outreach and public engagement work package (WP7) and an ethics work package (WP8).
The research work carried out and the main results obtained by each ESR are as follows. A main result of ESR1’s work has been the activity increase, while at the same time suppressing thermal decomposition, of a benzimidazolidene-based Z-selective olefin metathesis catalyst. The aim of ESR2 is the development of efficient catalytic systems for the synthesis of drugs and/or biologically active molecules via the asymmetric Rh-catalysed hydroaminomethylation of alkenes and he has focused on the optimization of this protocol for the synthesis of tolterodine. The work of ESR3 has elucidated the reaction mechanism of the alkali metal-catalysed addition of P-H functionalities onto alkynes through the use of DFT calculations. A major result of ESR4’s work was the increased catalytic performance upon grafting a ligand on graphene oxide for the Henry reaction. ESR5 was able to develop an unprecedented stoichiometry process with a C-C bond formation from a C-F substrate. ESR6 was able to evidence a new reaction pathway for s-bock metal amidinate complexes where CO2 reacts in two different ways, namely a with hydride ligand to produce a formate and with the amidinate central C atom to produce a carbonate. ESR7 was able to synthesize two photoisomerisable ligands for photoswitcheable catalysis. ESR8 was able to isolate a model anionic tetrahydride system of the previously suspected resting state of iridium-catalysed polar substrate hydrogenation. ESR9 has been able to efficiently retain the metal nanoparticle catalyst embedded in the core of hierarchically precise amphiphilic crosslinked polymers for several cycles by modifying the core-anchored stabilizing groups from phosphine to phosphine oxide. ESR10 was able to construct functionalized Janus dendrimer decorated with solubilizing groups on one side and Ru-based complexes for olefin metathesis (OM) catalysis on the other side. ESR11 has synthesised a few new functionalized ionic liquids and investigated the effect of the functionality on the catalytic activity in the hydrogenation of unsaturated substrates. The project of ESR 12 aims at anchoring carboranyl bisphosphine ligands on the surface of dendrimers for use in catalysis and is optimizing the conditions leading to quantitative grafting. ESR13 has obtained a doubly functionalized dendrimer, one function being suitable for catalysis, the other one inducing solubility in supercritical CO2. ESR14 has revealed a few unexpected transformations from the interaction of ruthenium pre-catalyst with germanes and developed a very efficient catalytic protocol for the hydrosilylation of nitriles. ESR15 has carried out combined experimental and computational investigations to optimise the CO2 one-electron reduction and spin localisation onto the carbon atom though the use of a frustrated Lewis acid/base pair systems using bulky NHCs and boranes, aiming at the photocatalyzed direct carboxylation of aliphatic C-H bonds under mild conditions. These results have been disseminated so far by four open access publications and by oral and/or poster presentations by the ESRs at three international meetings. Two of these were organized as part of the CCIMC projects (Cutting-Edge Homogeneous Catalysis, CEHC), namely CEHC-1 (online, May 2021) and CEHC-2 (Leipzig, April 2022), while the third one (4th HC3A, Barcelona, January 2022) was an independent meeting attended by all ESRs. Each ESR has also disseminated his/her results at other meetings, including but not restricted to the internal meeting of the Graduate Schools of the ESRs’ Universities. The ITN activities are regularly communicated to different target groups through the CCIMC website, through periodical Newsletters (ca. 4 per year), and through Twitter, LinkedIn and Instagram accounts.
The activity in WP2 has led to the fabrication of 9 new ligands. Work in WP3 has resulted in the development of 12 new molecular and 6 new supported pre-catalysts. The activity in WP4 has produced one in-depth mechanistic study, has revealed one new transformation involving the formation of a C-C bond by activation of a substrate C-F bond and one new process involving CO2 activation. Finally, numerous catalysed transformations have been investigated with the newly developed ligands and pre-catalysts, including four optimized processes in new confined media. In particular, 5 catalysed transformations were improved with respect to the state-of-the-art, either in terms of higher catalyst stability (turnover number), activity (turnover frequency), selectivity (lower content of undesired by-products) or simpler work-up procedures through confinement. By the end of the CCIMC project, it is hoped to at least double these numbers. It is also hoped that, after completing the secondment periods of the ESRs at the Partner institutions, a few of the developed processes will lead to intellectual protection and commercialization.