Putting Low Coordination into Practice by the Exploration of Metal-sigma-Interactions: Fundamentals, New Catalysts and Catalysis for New Materials

Lead Research Organisation: University of Oxford
Department Name: Oxford Chemistry

Abstract

The manipulation of chemical bonds to provide materials and chemicals of intrinsic value in the most energy and resource efficient way is at the heart of Chemistry. Catalysis is a cornerstone of this endeavour, contributing directly to the chemical industry in the UK (it is estimated that ~ 75% of all chemicals require catalysts in their manufacture), a manufacturing sector that generates ~21% of UK GDP. Transition metal-based systems play a central role in catalysis, often offering mechanistically distinct routes to molecules that could not be made by other means. The molecules thus produced may be of very high value/low volume, e.g. an intermediate in sophisticated synthetic route to a pharmaceutical; or lower relative value/high volume, e.g. polyolefins from fossil-resource derived hydrocarbons. The design, construction and implementation of new catalysts that offer step-changes in chemical manufacturing capability, in concert with improving the fundamental understanding of how chemical bonds can be manipulated, is thus central to: sustainable manufacturing, energy and resource security, and healthcare.

This Fellowship will allow for the study of two highly complementary strands of catalysis discovery, development and application, that capitalise on exciting emerging results from the Weller group. The scientific aim of the Fellowship is to develop, and harness in real-world applications, the fundamental and catalytic chemistry associated with the synthesis, characterisation and utilisation of metal sigma-complexes. It is both fundamental and applied in scope, broad in its vision, and will allow for the opening up of new areas in organometallic chemistry and main-group materials chemistry. Such challenging goals would have been unreasonable until very recently, but the breakthroughs in the applicant's laboratories set the scene for these significant future developments in the field. The programme will push back the limits of what can be achieved in the synthesis of reactive organometallic compounds, their use in catalysis for the manufacture of new, and exciting, types of polymeric materials and the efficient utilisation of fossil-resource derived chemical feedstocks (alkanes) and catalysts for fine chemicals synthesis (C-H activation).

Planned Impact

The manipulation of chemical bonds to provide materials and chemicals of intrinsic value in the most energy and resource efficient way is at the heart of Chemistry. Catalysis is a cornerstone of this endeavour, contributing directly to the chemical industry in the UK (it is estimated that ~ 75% of all chemicals require catalysts in their manufacture), a manufacturing sector that generates ~21% of UK GDP. Transition metal-based systems play a central role in catalysis, often offering mechanistically distinct routes to molecules that could not be made by other means. The molecules thus produced may be of very high value/low volume, e.g. an intermediate in a sophisticated synthetic route to a pharmaceutical; or lower relative value/high volume, e.g. polyolefins from fossil-resource derived hydrocarbons. The design, construction and implementation of new catalysts that offer step-changes in chemical manufacturing capability, in concert with improving the fundamental understanding of how chemical bonds can be manipulated, is therefore central to: sustainable manufacturing, energy and resource security, and healthcare.

The Fellowship described will enable the exploitation of recent transformative discoveries made by Weller in transition metal-sigma alkane / borane complexes to explore new areas related to these discoveries with particular emphasis on making significant discoveries in catalytic science. Knowledge gained from fundamental studies will be used to develop new catalysts capable of challenging C-H activation chemistry and the tailored production of, as yet unexplored, group 13/15 polymers and electronic materials. The programme will push back the limits of what can be achieved in the synthesis of reactive organometallic compounds, their use in catalysis for the manufacture of new, and exciting, types of polymeric materials and the efficient utilisation of fossil-resource derived chemical feedstocks (alkanes) and catalysts for fine chemicals synthesis (C-H activation). Its award will retain the momentum and competitive-edge gained over competitors in these fields, principally the USA, Japan and Germany. The results that flow from this Fellowship will have impact upon:

1) UK Industry. The proposed work will contribute to the development of atom efficient processes based on catalytic C-H activation. This will benefit the UK Chemicals Sector by responding to growing environmental pressures for sustainable synthesis and moving away from current more wasteful methods based on preactivated feedstocks, e.g. those containing C-halogen rather than C-H bonds. The studies to enable the development of highly efficient metal-catalyzed dehydrocoupling routes to main-group polymeric materials, a novel class of inorganic polymeric materials that are isoelectronic with polyolefins, will offer the prospect of developing new polymers with important potential uses and commercial applications.

2) Wider Society. The development of sustainable chemical synthesis based on C-H activation will also lead to benefits for the wider public. This approach will lessen the environmental impact associated with the production of chemical commodities. As well as bulk chemical production, such entities also underpin a range of fine chemicals found in pharmaceuticals, agrochemicals and other technological materials that society consumes in increasing volumes, while demanding the means of production be placed on a sustainable footing.

The synthesis of new materials which show potentially very useful properties, the development of new catalytic methodologies both specific to this project and, in a more general sense, are also measurable benefits that will arise from this Fellowship. The development of new efficient catalytic techniques that not only allow new technologically important materials relevant to societal and technology requirements to be made, but do this to order and with minimal waste, is of clear importance.

Publications

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Adams G (2018) POP-type ligands: Variable coordination and hemilabile behaviour in Coordination Chemistry Reviews

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Benjamin SL (2016) [Pd4(µ3-SbMe3)4(SbMe3)4]: A Pd(0) Tetrahedron with µ3-Bridging Trimethylantimony Ligands. in Journal of the American Chemical Society

 
Description Diamond Light Source PhD Studentships Flow-Diffraction-GCMS
Amount £116,000 (GBP)
Organisation Diamond Light Source 
Sector Academic/University
Country United Kingdom
Start 10/2019 
End 09/2023