The project so far has focused on established a broad number of catalyst systems, involving ligand development, exploration of novel transition metal fragments, and screening of their proficiency in waste-free catalytic protocols.
This has led to a number of high-tier publications, two of which are described here. In the first, we were able to develop a new family of ligands based on germanium(II) binding centres. Using simple ligand design concepts, we were able to modulate the bonding nature of these systems. Then, in cooperation with a low-valent nickel centre, we could show that this allows for modulating the energy of reversible dihydrogen activation. This is a key finding for the project, directly demonstrating that the concept laid out in our original proposal are indeed feasible. The energies of this process were quantified by in-depth kinetic methods, and corroborated by computational modelling. Finally, this 'tuneability' was coupled to a catalytic process: we found the all systems can achieve the dehydrocoupling of silanes, with reaction rates depending on the nature of the ligand system.
In the second publication, we demonstrated a facile method for accessing bimetallic Ga-Ni systems, which feature our develop chelating ligands. This is key in stabilising these systems, and driving their chemistry. Here, we found that systems reversibly and cooperatively activate dihydrogen, and can achieve the catalytic selective semi-hydrogenation of alkynes to alkenes. In-depth kinetic and computation studies shed light on the unique cooperative mechanism at play in this system, confirming our hypotheses at the project outset.
