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).
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
Adams G
(2018)
Dehydropolymerization of H 3 B·NMeH 2 To Form Polyaminoboranes Using [Rh(Xantphos-alkyl)] Catalysts
in Journal of the American Chemical Society
Adams G
(2018)
POP-type ligands: Variable coordination and hemilabile behaviour
in Coordination Chemistry Reviews
Adams GM
(2019)
Dehydropolymerization of H3B·NMeH2 Using a [Rh(DPEphos)]+ Catalyst: The Promoting Effect of NMeH2.
in ACS catalysis
Azpeitia S
(2020)
Si-C(sp3) bond activation through oxidative addition at a Rh(i) centre.
in Dalton transactions (Cambridge, England : 2003)
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
Boyd T
(2020)
Rücktitelbild: A Structurally Characterized Cobalt(I) s-Alkane Complex (Angew. Chem. 15/2020)
in Angewandte Chemie
Boyd T
(2020)
Back Cover: A Structurally Characterized Cobalt(I) s-Alkane Complex (Angew. Chem. Int. Ed. 15/2020)
in Angewandte Chemie International Edition
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)
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)
Chadwick FM
(2016)
Selective C-H Activation at a Molecular Rhodium Sigma-Alkane Complex by Solid/Gas Single-Crystal to Single-Crystal H/D Exchange.
in Journal of the American Chemical Society
Chadwick FM
(2016)
A Rhodium-Pentane Sigma-Alkane Complex: Characterization in the Solid State by Experimental and Computational Techniques.
in Angewandte Chemie (International ed. in English)
Chadwick FM
(2017)
Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates.
in Chemical science
Colebatch A
(2017)
Fluoroarene Complexes with Small Bite Angle Bisphosphines: Routes to Amine-Borane and Aminoborylene Complexes
in European Journal of Inorganic Chemistry
Colebatch AL
(2018)
A General, Rhodium-Catalyzed, Synthesis of Deuterated Boranes and N-Methyl Polyaminoboranes.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Colebatch AL
(2019)
Amine-Borane Dehydropolymerization: Challenges and Opportunities.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Coxon TJ
(2017)
Exploiting Carbonyl Groups to Control Intermolecular Rhodium-Catalyzed Alkene and Alkyne Hydroacylation.
in Journal of the American Chemical Society
Dietz M
(2019)
The [Rh(Xantphos)]+ catalyzed hydroboration of diphenylacetylene using trimethylamine-borane
in Inorganica Chimica Acta
Furfari SK
(2021)
Selectivity of Rh···H-C Binding in a s-Alkane Complex Controlled by the Secondary Microenvironment in the Solid State.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Grigoropoulos A
(2018)
Encapsulation of Crabtree's Catalyst in Sulfonated MIL-101(Cr): Enhancement of Stability and Selectivity between Competing Reaction Pathways by the MOF Chemical Microenvironment.
in Angewandte Chemie (International ed. in English)
Johnson A
(2019)
A d10 Ag(i) amine-borane s-complex and comparison with a d8 Rh(i) analogue: structures on the ?1 to ?2:?2 continuum.
in Dalton transactions (Cambridge, England : 2003)
Krämer T
(2023)
Solid-State Confinement Effects in Selective exo -H/D Exchange in the Rhodium s-Norbornane Complex [(Cy 2 PCH 2 CH 2 PCy 2 )Rh(? 2 :? 2 -C 7 H 12 )][BAr F 4 ]
in Helvetica Chimica Acta
Kumar A
(2016)
The Simplest Amino-borane H 2 B=NH 2 Trapped on a Rhodium Dimer: Pre-Catalysts for Amine-Borane Dehydropolymerization
in Angewandte Chemie
Kumar A
(2016)
The Synthesis, Characterization and Dehydrogenation of Sigma-Complexes of BN-Cyclohexanes.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Kumar A
(2016)
The Simplest Amino-borane H2 B=NH2 Trapped on a Rhodium Dimer: Pre-Catalysts for Amine-Borane Dehydropolymerization.
in Angewandte Chemie (International ed. in English)
Martínez-Martínez AJ
(2019)
Reversible Encapsulation of Xenon and CH2 Cl2 in a Solid-State Molecular Organometallic Framework (Guest@SMOM).
in Angewandte Chemie (International ed. in English)
Martínez-Martínez AJ
(2020)
Solid-State Molecular Organometallic Catalysis in Gas/Solid Flow (Flow-SMOM) as Demonstrated by Efficient Room Temperature and Pressure 1-Butene Isomerization.
in ACS catalysis
Martínez-Martínez AJ
(2018)
Modulation of s-Alkane Interactions in [Rh(L2)(alkane)]+ Solid-State Molecular Organometallic (SMOM) Systems by Variation of the Chelating Phosphine and Alkane: Access to ?2,?2-s-Alkane Rh(I), ?1-s-Alkane Rh(III) Complexes, and Alkane Encapsulation.
in Journal of the American Chemical Society
Martínez-Martínez AJ
(2019)
Solvent-free anhydrous Li+, Na+ and K+ salts of [B(3,5-(CF3)2C6H3)4]-, [BArF4]-. Improved synthesis and solid-state structures.
in Dalton transactions (Cambridge, England : 2003)
McKay A
(2018)
Controlling Structure and Reactivity in Cationic Solid-State Molecular Organometallic Systems Using Anion Templating
in Organometallics
McKay AI
(2019)
Room Temperature Acceptorless Alkane Dehydrogenation from Molecular s-Alkane Complexes.
in Journal of the American Chemical Society
McKay AI
(2020)
Synthesis of Highly Fluorinated Arene Complexes of [Rh(Chelating Phosphine)]+ Cations, and their use in Synthesis and Catalysis.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Spearing-Ewyn EAK
(2019)
The role of neutral Rh(PONOP)H, free NMe2H, boronium and ammonium salts in the dehydrocoupling of dimethylamine-borane using the cationic pincer [Rh(PONOP)(?2-H2)]+ catalyst.
in Dalton transactions (Cambridge, England : 2003)
Sung S
(2017)
Convergent (De)Hydrogenative Pathways via a Rhodium a-Hydroxylalkyl Complex
in Organometallics
Theron R
(2016)
Simultaneous Orthogonal Methods for the Real-Time Analysis of Catalytic Reactions
in ACS Catalysis
Turner J
(2018)
Iron Precatalysts with Bulky Tri(tert-butyl)cyclopentadienyl Ligands for the Dehydrocoupling of Dimethylamine-Borane.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Wang X
(2017)
Oligomeric aminoborane precursors for the chemical vapour deposition growth of few-layer hexagonal boron nitride
in CrystEngComm
| Description | Diamond Light Source PhD Studentships Flow-Diffraction-GCMS |
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