Novel Base Metal Catalysts based on Dinuclear Organometallics for Sustainable Chemistry and Energy

Molecular transition metal catalysts typically rely on the use of platinum group metals, whose availability and toxicity are increasing concerns in the context of sustainability. The much more benign and available base metals represent appealing alternatives if we had strategies available for imparting 2 electron redox chemistry on them to effect selective element-element bond rearrangements without free radical intermediates. Current focus on achieving this lies on functional organic ligands that either actively participate in a step of the catalytic cycle (e.g. proton relays) or function as electron buffers (redox-active ligands). These strategies have been derived from observing such effects on noble metals, and only in very few cases have been successfully transferred to base metals. A general difficulty with this functional ligand design is that the ligand electronics and sterics have to be precisely tailored to a-priory unknown intermediates to effect the desired cooperativity.

In this project, we will explore an alternative approach based on intermetallic cooperativity in precisely engineered dinuclear base metal complexes. Natural metalloenzymes have evolved to use a flexible ensemble of base metals for multi-electron catalysis at their active sites, so with the right ligand scaffold this must be feasible in synthetic systems too. Based on encouraging literature precedence and our recent work on pentalenides, we will develop synthetic methodologies to syn-dinuclear half-sandwich complexes of bridging pi ligands that hold two base metals in the right position for synergistic cooperativity in catalysis. These compounds hold great potential for replacing precious metals in existing applications, and promise new catalytic methodologies that are impossible with existing mononuclear catalysts.

The successful candidate will take over from a finishing PhD student in our lab, and synthesize novel homo- and hetero-dinuclear pentalide complexes of Mn, Fe, Co, Ni and Cu with a variety of ancillary ligands, and investigate their redox and ligand substitution chemistry with the aim of using them reductive catalysis (hydrogenations, hydrogen-borrowing, proton reduction, carbonylations, etc.) following a mechanism-guided approach based on operando spectroscopy and electrochemistry.

Training:

This is an opportunity to join a thriving research group of 8 PhD students working on various aspects of applied catalysis. Due to the multi-disciplinary nature of our research group, you will not only receive state-of-the-art training in your project subjects but also be exposed to a range of different topics. A particularly exciting possibility will be using and learning about FlowNMR spectroscopy, a separate work program in our group which has recently lead to the establishment of a dedicated ₤1.3m Dynamic Reaction Monitoring Facility at Bath that we have access to. We actively support participation in national and international meetings and conferences (as appropriate) to raise awareness of developments in related areas, and to provide students with opportunities for developing wider presentation and networking skills. You will have the chance to attend some of the many research seminars happening in our department throughout your PhD, and you are strongly encouraged to make good use of the large variety of PG skill courses offered by the University’s Researcher Development Unit. As part of the Centre for Sustainable Chemical Technologies, you will also have the possibility of partaking in a wide range of professionally organised public engagement and outreach activities.

Anticipated start date: 1 October 2018.

Informal enquiries should be addressed to Dr Ulrich Hintermair, [Email Address Removed]

Formal applications should be made via the University of Bath’s online application form – lhttps://www.bath.ac.uk/samis/urd/sits.urd/run/siw_ipp_lgn.login?process=siw_ipp_app&code1=RDUCH-FP01&code2=0012

More information about applying for a PhD at Bath may be found here:
http://www.bath.ac.uk/guides/how-to-apply-for-doctoral-study/