Photoactivated Organometallic Catalysts for Hydrosilylation

Cross–linked silicones are speciality polymers used for wide variety of high value applications, for example: as release liners (e.g. sticky notes), high–performance tubing, medical elastomers, high–speed curing (dentistry), electronics and fire–retardant cabling. These technologically important polymers are made by hydrosilylation of an alkene with a silicone–based precursor, using a catalyst that is activated by photolysis. The current state-of-the-art catalyst is a Pt–based organometallic complex. However, despite its commercial use, little is known about the mechanism of catalysis; while the development of alternative catalysts that are cheaper, more sustainable and less hazardous is not well-developed.

This collaborative project with Johnson Matthey will directly address these gaps in fundamental and applied knowledge. It will start by looking at understanding how the current state of the art catalyst works, by using in situ NMR photolysis techniques combined with synthetic, kinetic and catalytic studies. Informed by these studies, new group 8, 9 and 10 photoactivated organometallic systems will then be designed, synthesised and tested in catalysis. These synthetic, NMR and mechanistic studies will progress to develop a new suite of catalysts that offer improved performance for photoactivated hydrosilylation. Close interactions with Johnson Matthey throughout the project will allow promising systems to be developed in an industrial context. The results of these applied studies will be fed back into new synthetic and mechanistic studies performed at York.

This PhD offers an exciting new collaboration that blends fundamental organometallic chemistry with a strong trajectory to use discoveries made in the project in an industrial setting. It brings together world–leading research groups in organometallic synthesis, NMR, catalysis and mechanism with the expertise of Johnson Matthey: industry leaders in developing organometallics for catalysis. The successful PhD candidate will be collaborative, able to focus on the fine detail while keeping a broader perspective, enjoy challenging organometallic synthesis, and keen to learn new techniques / problem solve. While the PhD student will be based in the York Organometallic Synthesis, Catalysis and Mechanism laboratories, there will be opportunities spend extended periods at Johnson Matthey for catalyst development and evaluation.

The Weller group are moving from Oxford to York in January 2020.

All research students follow our innovative Doctoral Training in Chemistry (iDTC): cohort-based training to support the development of scientific, transferable and employability skills. All research students take the core training package which provides both a grounding in the skills required for their research, and transferable skills to enhance employability opportunities following graduation. Core training is progressive and takes place at appropriate points throughout a student’s higher degree programme, with the majority of training taking place in Year 1. In conjunction with the Core training, students, in consultation with their supervisor(s), select training related to the area of their research. Project specific training includes Air sensitive organometallic synthesis, Advanced NMR techniques (especially insitu photolysis) and photoredox catalysis, Kinetics and mechansim and other analytical techniques (e.g. single crystal x-ray diffraction).

The Department of Chemistry holds an Athena SWAN Gold Award and is committed to supporting equality and diversity for all staff and students. The Department strives to provide a working environment which allows all staff and students to contribute fully, to flourish, and to excel: https://www.york.ac.uk/chemistry/ed/.

This PhD will formally start on 1 October 2020. Induction activities will start on 28 September.