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 York
Department Name: 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).
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.
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
Azpeitia S
(2020)
Si-C(sp3) bond activation through oxidative addition at a Rh(i) centre.
in Dalton transactions (Cambridge, England : 2003)
Boyd TM
(2020)
A simple cobalt-based catalyst system for the controlled dehydropolymerisation of H3B·NMeH2 on the gram-scale.
in Chemical communications (Cambridge, England)
Boyd TM
(2020)
A Structurally Characterized Cobalt(I) s-Alkane Complex.
in Angewandte Chemie (International ed. in English)
Brodie CN
(2021)
Controlled Synthesis of Well-Defined Polyaminoboranes on Scale Using a Robust and Efficient Catalyst.
in Journal of the American Chemical Society
Bukvic A
(2021)
A Series of Crystallographically Characterized Linear and Branched s-Alkane Complexes of Rhodium: From Propane to 3-Methylpentane
in Journal of the American Chemical Society
Bukvic AJ
(2020)
Tolerant to air s-alkane complexes by surface modification of single crystalline solid-state molecular organometallics using vapour-phase cationic polymerisation: SMOM@polymer.
in Chemical communications (Cambridge, England)
Doyle L
(2022)
Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane s-Alkane Complex
in Organometallics
Doyle LR
(2022)
MicroED characterization of a robust cationic s-alkane complex stabilized by the [B(3,5-(SF5)2C6H3)4]- anion, via on-grid solid/gas single-crystal to single-crystal reactivity.
in Dalton transactions (Cambridge, England : 2003)
Description | "In-Crystallo" Solid-State Molecular Organometallic Chemistry of Methane, Ethane and Propane. Synthesis, Structures and Catalysis in Single-Crystals |
Amount | £526,463 (GBP) |
Funding ID | EP/W015552/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start | 06/2022 |
End | 12/2025 |
Description | Making Xenon a Ligand Using Solid-State Molecular Organometallic Chemistry |
Amount | £198,181 (GBP) |
Funding ID | RPG-2020-184 |
Organisation | The Leverhulme Trust |
Sector | Charity/Non Profit |
Country | United Kingdom |
Start | 01/2021 |
End | 09/2024 |
Description | Photoactivated Catalysts for Hydrosilylation |
Amount | £87,500 (GBP) |
Funding ID | JM13493 |
Organisation | Johnson Matthey |
Sector | Private |
Country | United Kingdom |
Start | 09/2020 |
End | 03/2024 |
Description | Collaboration with Professor Simon Duckett on hyper polarisation |
Organisation | University of York |
Department | Department of Chemistry |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | Organometallic chemistry and synthesis and catalysis |
Collaborator Contribution | Expertise in hyperpolarisition techniques in NMR spectroscopy |
Impact | A. Johnson, C. G. Royle, C. N. Brodie, A. J. Martínez-Martínez, S. B. Duckett and A. S. Weller* ?2-Alkene Complexes of [Rh(PONOP-iPr)(L)]+ Cations (L = COD, NBD, ethene). Intramolecular Alkene-Assisted Hydrogenation and a Dihydrogen Complex [Rh(PONOP-iPr)(?-H2)]+ Inorg. Chem. 2021, doi.org/10.1021/acs.inorgchem.0c03687 |
Start Year | 2020 |
Description | Industry funded PhD studentship with Johnson Matthey |
Organisation | Johnson Matthey |
Department | Johnson Matthey Technology Centre |
Country | United Kingdom |
Sector | Private |
PI Contribution | PhD studentship in photochemical techniques in catalysis and mechanism. |
Collaborator Contribution | Funding of a PhD student |
Impact | None so far |
Start Year | 2020 |