Context. New catalytic processes that support the EPSRC theme of 'Manufacturing the Future' also overlap with the Maintained areas of Synthetic Coordination Chemistry and Catalysis within the EPSRC Physical Sciences portfolio, as well has having tangential contact with other areas such as Synthetic Organic Chemistry. Discovery of these catalysts, guided by the PI's advanced understanding of topology, is a new approach and builds on the considerable success to date within the Subject Group, which has also been highly productive. It is also related to the previous grant award (EP/M023834/1), which focused on fundamental synthesis of 3d/4f coordination clusters, which act as this type of catalyst.

Importance. The discovery of new, atom-efficient and energy efficient catalytic processes is critical to sustaining the synthetic chemistry required for applications in the pharmaceutical industry and other concerns which use organic chemistry. Laboratories-as-factories are a key strand in European and UK research efforts as sustainable, waste-free - 'reagentless' - catalysis is correctly seen as being the direction of travel for the modern chemical industry. The work outlined in this proposal will address this area directly in a practical manner while also illuminating the fundamental science that underpins these advances. The expected outcome of the proposed research will be the discovery of new catalysts that are clean and green. At a fundamental level, it will enhance our understanding of molecular interactions at the level of the topological description as well as the level of individual catalytic mechanisms.

Methodology. The purpose of this project is to exploit the PI's advanced understanding of topology as a guiding principle to define the compositional space within which new efficient and green catalysts will be developed. The topology of a CC is independent of the ligand set, metal centre and oxidation state. Very often, desirable properties, in this case, catalytic properties, are retained as long as the topology is invariant; this contrasts with organometallic catalysts, where the electronic structure and reactivity is driven by the properties of the ligand field. With this insight, a wider range of catalytic compositions are therefore available and it is within this expanded compositional space - with respect to the nature of the metal and the ligand set - that the synthetic methods developed in the PI's laboratory will be directed. Rapid synthesis within this topological-compositional space will be accompanied by screening as catalysts, with viable catalysts being then mechanistically investigated. The mechanistic investigation will provide the fundamental science required to confirm the topological underpinning of the methodology.

Specific initial reaction targets for catalysis include

• Michael addition¹
• A³ coupling²
• Electrocyclic reaction³
• Enantioselective Povarov⁴

as these reactions are particularly amenable to Lewis acid catalysis. Enantiocontrol will be effected through conditioning the energy of the transition state topologically.

Training. The student will be trained in several interdisciplinary areas bordering inorganic, organic and materials chemistry and X-Ray crystallography. The student will receive the Health and Safety Induction and be able to attend MChem modules to gain further knowledge. The student will be properly trained in preparing research articles and proposals, citation management and will attend the Departmental seminars. The student will gain skills by visiting other laboratories and attending International and National conferences.