Hydrophosphination Catalysis Using Low-Coordinate Iron Complexes
Lead Research Organisation:
University of Nottingham
Department Name: Sch of Chemistry
Abstract
Organophosphorus compounds are one of the most important species in chemistry, driving critical advances in areas such as medicine, metal extraction, nuclear fuel processing, lubricants, agrochemicals, materials and supramolecular chemistry. Their wide use as ligands to transition metals underpins many modern homogeneous catalytic processes, for example in metal-catalysed cross-coupling, alkene metathesis and C-H activation reactions. Classic synthetic routes to phosphines often display poor functional group tolerance, side product formation, and use a significant number of steps including stoichiometric amounts of additives, toxic metal reagents and protecting groups. These limitations lead to copious waste, representing a problem for atom economy.
Hydrophosphination reactions involve the addition of a P-H moiety across an unsaturated bond, and offer the potential for 100% atom efficiency with the opportunity to generate significant complexity in the organophosphorus products using relatively simple starting materials. In particular, the hydrophosphination of C=X (X = O, N, S) bonds is a powerful way to introduce heteroatom functionality into products, but remains poorly explored due to the paucity of suitable catalytic complexes, competing side reactions and catalyst poisoning. Thus, the use of this reaction as a convenient strategy to heterofunctionalised phosphorus compounds has not been exploited. Driven by major global efforts towards chemical synthesis using earth-abundant and non-toxic metals, we propose to deliver a new approach for the syntheses of organophosphorus compounds using iron complexes as pre-catalysts for the hydrophosphination of heterocumulene compounds. Significantly, our complexes can catalyse novel diinsertion pathways for this reaction, which are very rare and usually difficult to control. These new reaction pathways have the power to unlock new reactions and synthetic methodologies.
We will explore this hydrophosphination chemistry and use unexplored substrates to deliver new families of organophosphorus compounds and develop a rational approach to control reactivity and regioselectivity through the manipulation of the structure of the catalyst and the reaction conditions. This chemistry will be used to synthesise specific organophosphorus targets and the elucidation of the mechanisms for this catalysis will provide experimental and theoretical data to inform new reaction strategies that may be developed in new catalytic reactions. This research programme will thus deliver a wealth of fundamental knowledge in addition to a bank of new organophosphorus compounds, which will be made available to researchers in academia and industry.
This research programme has the potential to have significant impact for a broad range of academic and industrial applications due to the extensive properties and potential uses of a range of very different organophosphorus species. We envisage that our approach to the catalysis of hydrophosphination will impact a range of hydroelementation reactions and may impact other methodologies such as homologation, polymerisation and selective oligomerisation reactions.
Hydrophosphination reactions involve the addition of a P-H moiety across an unsaturated bond, and offer the potential for 100% atom efficiency with the opportunity to generate significant complexity in the organophosphorus products using relatively simple starting materials. In particular, the hydrophosphination of C=X (X = O, N, S) bonds is a powerful way to introduce heteroatom functionality into products, but remains poorly explored due to the paucity of suitable catalytic complexes, competing side reactions and catalyst poisoning. Thus, the use of this reaction as a convenient strategy to heterofunctionalised phosphorus compounds has not been exploited. Driven by major global efforts towards chemical synthesis using earth-abundant and non-toxic metals, we propose to deliver a new approach for the syntheses of organophosphorus compounds using iron complexes as pre-catalysts for the hydrophosphination of heterocumulene compounds. Significantly, our complexes can catalyse novel diinsertion pathways for this reaction, which are very rare and usually difficult to control. These new reaction pathways have the power to unlock new reactions and synthetic methodologies.
We will explore this hydrophosphination chemistry and use unexplored substrates to deliver new families of organophosphorus compounds and develop a rational approach to control reactivity and regioselectivity through the manipulation of the structure of the catalyst and the reaction conditions. This chemistry will be used to synthesise specific organophosphorus targets and the elucidation of the mechanisms for this catalysis will provide experimental and theoretical data to inform new reaction strategies that may be developed in new catalytic reactions. This research programme will thus deliver a wealth of fundamental knowledge in addition to a bank of new organophosphorus compounds, which will be made available to researchers in academia and industry.
This research programme has the potential to have significant impact for a broad range of academic and industrial applications due to the extensive properties and potential uses of a range of very different organophosphorus species. We envisage that our approach to the catalysis of hydrophosphination will impact a range of hydroelementation reactions and may impact other methodologies such as homologation, polymerisation and selective oligomerisation reactions.
Planned Impact
Organophosphorus compounds are one of the most important species in chemistry, underpinning critical advances in many areas such as catalysis, medicine, metal extraction, nuclear fuel processing, agrochemicals and lubricants. While the current methodologies to phosphines are effective, synthetic routes often display poor functional group tolerance, use a number of steps, protecting groups and coupling reactions, which gives rise to copious waste which is a problem for atom economy. This research programme will deliver a new approach using iron complexes to catalyse the hydrophosphination of heterocumulenes accessing novel reaction pathways to deliver new families of organophosphorus compounds of significant impact in the above applications. The beneficiaries will be the Commercial Sector, the Public Sector, and Society, as detailed below.
Commercial Sector: In the short term, industrial organisations will benefit from new samples of organophosphorus compounds with uses in areas such as catalysis, medicine, metal extraction, nuclear fuel processing, agrochemicals and lubricants. In the long term, this research, although fundamental in nature, has the potential to inform new, more efficient catalytic methodologies using abundant and environmentally benign metals, which has the capability to reduce waste and improve sustainability. R&D is crucial to the UK chemicals industry, and its growth and competitiveness in the world market can only be sustained by exploiting new catalysts and processes from fundamental research. Industry will also benefit from the inspiration of workers for its labour force (see below).
Public Sector/Knowledge Base: This research will feed into the EPSRC Prosperity Outcome Productive Nation (Delivery Plan 2016-20), addressing the EPSRC Catalysis and Sustainable Chemistry Priority Areas, and EPSRC Theme Manufacturing the Future, benefitting policy makers, funding bodies and academic institutions in the short through to long term by providing clear evidence of the value of fundamental, internationally leading research in the UK which aligns with the EPSRC ideals. This research will be of immediate benefit to academics interested in synthesis, structure, reaction catalysis and methodology, theory, green chemistry and new phosphines for myriad uses. In the long term this project will provide a platform for future technological exploitation, both in academia and industry. The EPSRC/RSC report "The Economic Benefits of Chemistry Research to the UK" highlights the contribution that cutting-edge chemistry research makes to the UK science base. The academic investigators will see significant personal career development through this collaborative research programme, broadening their knowledge, particularly through exposure to Industrial Stakeholders and their research. This project will provide a wealth of scientific and training and transferrable skills, benefitting the PDRA.
Society: In the short term society will benefit from an increased awareness of chemistry through outreach activities. If the UK is to be competitive in the global market, public support for scientific research is essential. Furthermore, a general public with a good understanding of science and technology will be better equipped to provide an adaptable labour force with the skills and flexibility to deal with technological change. The Social Market Foundation's "In the Balance: the STEM Human Capital Crunch" report states that by 2020 "a 49% increase in STEM graduates would be required if employment requirements are to be met from domestic supply." Thus, in the long term the next generation of STEM students will help to secure future prosperity, from the inspiration of people to take an interest in science. In the long term, the public will benefit from the generation of new chemicals and new industrial processes resulting from this research programme. These benefits may involve new products, reduced costs, or from improved sustainability.
Commercial Sector: In the short term, industrial organisations will benefit from new samples of organophosphorus compounds with uses in areas such as catalysis, medicine, metal extraction, nuclear fuel processing, agrochemicals and lubricants. In the long term, this research, although fundamental in nature, has the potential to inform new, more efficient catalytic methodologies using abundant and environmentally benign metals, which has the capability to reduce waste and improve sustainability. R&D is crucial to the UK chemicals industry, and its growth and competitiveness in the world market can only be sustained by exploiting new catalysts and processes from fundamental research. Industry will also benefit from the inspiration of workers for its labour force (see below).
Public Sector/Knowledge Base: This research will feed into the EPSRC Prosperity Outcome Productive Nation (Delivery Plan 2016-20), addressing the EPSRC Catalysis and Sustainable Chemistry Priority Areas, and EPSRC Theme Manufacturing the Future, benefitting policy makers, funding bodies and academic institutions in the short through to long term by providing clear evidence of the value of fundamental, internationally leading research in the UK which aligns with the EPSRC ideals. This research will be of immediate benefit to academics interested in synthesis, structure, reaction catalysis and methodology, theory, green chemistry and new phosphines for myriad uses. In the long term this project will provide a platform for future technological exploitation, both in academia and industry. The EPSRC/RSC report "The Economic Benefits of Chemistry Research to the UK" highlights the contribution that cutting-edge chemistry research makes to the UK science base. The academic investigators will see significant personal career development through this collaborative research programme, broadening their knowledge, particularly through exposure to Industrial Stakeholders and their research. This project will provide a wealth of scientific and training and transferrable skills, benefitting the PDRA.
Society: In the short term society will benefit from an increased awareness of chemistry through outreach activities. If the UK is to be competitive in the global market, public support for scientific research is essential. Furthermore, a general public with a good understanding of science and technology will be better equipped to provide an adaptable labour force with the skills and flexibility to deal with technological change. The Social Market Foundation's "In the Balance: the STEM Human Capital Crunch" report states that by 2020 "a 49% increase in STEM graduates would be required if employment requirements are to be met from domestic supply." Thus, in the long term the next generation of STEM students will help to secure future prosperity, from the inspiration of people to take an interest in science. In the long term, the public will benefit from the generation of new chemicals and new industrial processes resulting from this research programme. These benefits may involve new products, reduced costs, or from improved sustainability.
Organisations
Publications
Blundell TJ
(2020)
A transition metal-gallium cluster formed via insertion of "GaI".
in Chemical communications (Cambridge, England)
Huke C
(2021)
Catalyst-free Hydrophosphinylation of Isocyanates and Isothiocyanates under Low-Added-Solvent Conditions
in ACS Sustainable Chemistry & Engineering
Liu Y
(2021)
Group 11 m-Terphenyl Complexes Featuring Metallophilic Interactions.
in Inorganic chemistry
Nolla-Saltiel R
(2023)
Organoruthenium Complexes Containing Phosphinodicarboxamide Ligands
in Inorganics
Nolla-Saltiel R
(2020)
Hydrophosphination of Activated Alkenes by a Cobalt(I) Pincer Complex
in Advanced Synthesis & Catalysis
Ried ACA
(2020)
Corrigendum: A Highly Active Bidentate Magnesium Catalyst for Amine-Borane Dehydrocoupling: Kinetic and Mechanistic Studies.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Ried ACA
(2019)
A Highly Active Bidentate Magnesium Catalyst for Amine-Borane Dehydrocoupling: Kinetic and Mechanistic Studies.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Sharpe HR
(2018)
Selective reduction and homologation of carbon monoxide by organometallic iron complexes.
in Nature communications
South A
(2019)
Iron(II)-Catalyzed Hydroamination of Isocyanates
in Organometallics
Taylor LJ
(2019)
Low-coordinate first-row transition metal complexes in catalysis and small molecule activation.
in Dalton transactions (Cambridge, England : 2003)
Valentine AJ
(2022)
Slow magnetic relaxation in Fe(II) m-terphenyl complexes.
in Dalton transactions (Cambridge, England : 2003)
Valentine AJ
(2021)
Structural and electronic studies of substituted m-terphenyl lithium complexes.
in Dalton transactions (Cambridge, England : 2003)
Valentine AJ
(2022)
Structural and Electronic Studies of Substituted m-Terphenyl Group 12 Complexes.
in Organometallics
Description | - The activation and scission of CO to make new C4 rings, and mechanistic data - Hydrophosphination of carbodiimides which affords monoinsertion and some diinsertion compounds, of which data is still being processed - Extension to hydroamination chemistry, catalysed by low-coordinate iron(II) organometallics. This seems to be more difficult to control than the hydrophosphination, although the multiple insertions we will be reporting show excellent potential applicability if it can be controlled. - Electronic effects of the m-terphenyl ligands that will have impact beyond reactivity - Greener methods to hydrophosphination reactions |
Exploitation Route | New phosphorus compounds may be used by other researchers in areas such as ligands, organocatalysis, TM catalysis, lubricants, medicine. CO activation mechanisms may inform researchers about mechanisms for CO activation and Fischer Tropsch catalysis |
Sectors | Chemicals |
Description | Researchers are using the knowledge we have developed in their synthesis, characterisation and reactivity investigations. Outreach to schools and the general public Facilitating discussions with industrial partners |
Sector | Chemicals |
Impact Types | Societal,Economic |
Description | Difunctionalisation of Heterocumulenes: New Compounds from E-E' Addition |
Amount | £59,193 (GBP) |
Funding ID | RF-2021-102 |
Organisation | The Leverhulme Trust |
Sector | Charity/Non Profit |
Country | United Kingdom |
Start | 09/2021 |
End | 08/2022 |
Description | Driving CO Scission and Homologation Reactions Using Organometallic Complexes |
Amount | £179,837 (GBP) |
Funding ID | RPG-2021-183 |
Organisation | The Leverhulme Trust |
Sector | Charity/Non Profit |
Country | United Kingdom |
Start | 12/2021 |
End | 11/2024 |
Description | 4th Small Molecule Activation Conference |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Chemical discussions, questions. Started a collaboration with a research group in Spain |
Year(s) Of Engagement Activity | 2022 |
Description | AGICHEM 2021 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Postgraduate students |
Results and Impact | Questions and discussion. Participated in a workshop/sandpit during the conference |
Year(s) Of Engagement Activity | 2021 |
Description | Dalton North Meeting - Presentation by PDRA |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Regional |
Primary Audience | Postgraduate students |
Results and Impact | PDRA (Laurence Taylor) gave a presentation on recent work within the research group, leading to chemical discussion |
Year(s) Of Engagement Activity | 2019 |
Description | Expert Panel Member to Early Career Researchers, primarily women at the Women in Chemistry Conference 2019, University of Nottingham |
Form Of Engagement Activity | A formal working group, expert panel or dialogue |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Professional Practitioners |
Results and Impact | Expert panel member to postgraduate students, postdoctoral researchers and academics |
Year(s) Of Engagement Activity | 2019 |
Description | ISQCH Seminar Series, University of Zaragoza |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Postgraduate students |
Results and Impact | Discussion and question session afterwards |
Year(s) Of Engagement Activity | 2021 |
Description | Interview for Radleys Inspiring Women in Science Series |
Form Of Engagement Activity | A press release, press conference or response to a media enquiry/interview |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Public/other audiences |
Results and Impact | Interview with Radleys about me and my research |
Year(s) Of Engagement Activity | 2019 |
URL | https://www.radleys.com/blog/inspiring-women-in-science-an-interview-with-the-university-of-nottingh... |
Description | Invited Lecture at University of Lancaster |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Postgraduate students |
Results and Impact | Questions and discussion after lecture |
Year(s) Of Engagement Activity | 2022 |
Description | Invited lecture at the University of Lincoln |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Regional |
Primary Audience | Postgraduate students |
Results and Impact | Question and discussion. |
Year(s) Of Engagement Activity | 2022 |
Description | Invited talk at Cardiff University |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Local |
Primary Audience | Postgraduate students |
Results and Impact | Research seminar; disseminated research to members of the School of Chemistry |
Year(s) Of Engagement Activity | 2019 |
Description | Invited talk at Catalysis: from understanding to applications, Albi, France |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Postgraduate students |
Results and Impact | Dr Laurence Taylor (PDRA) invited to present at the Summer School |
Year(s) Of Engagement Activity | 2019 |
Description | Invited talk at Nottingham Trent University |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Local |
Primary Audience | Postgraduate students |
Results and Impact | Research seminar; disseminated research at the School of Chemistry |
Year(s) Of Engagement Activity | 2019 |
Description | Invited talk at Organometallic & Main Group Seminar Series, University of Oxford |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Local |
Primary Audience | Postgraduate students |
Results and Impact | Research Seminar, disseminated my research to the organometallic and main group researchers |
Year(s) Of Engagement Activity | 2019 |
Description | Invited talk at UCL |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Postgraduate students |
Results and Impact | Research seminar; disseminated research to the school of Chemistry |
Year(s) Of Engagement Activity | 2019 |
Description | Invited talk at University of Sussex |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Postgraduate students |
Results and Impact | Research seminar; disseminated research to the School of Chemistry |
Year(s) Of Engagement Activity | 2018 |
Description | Invited talk at the University of Central Lancashire |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Postgraduate students |
Results and Impact | Presentation of research at the School of Chemistry |
Year(s) Of Engagement Activity | 2018 |
Description | Invited talk at the University of Oxford |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Local |
Primary Audience | Postgraduate students |
Results and Impact | Research seminar; disseminated research to the School of Chemistry |
Year(s) Of Engagement Activity | 2020 |
Description | Invited talk at the University of St Andrews |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Postgraduate students |
Results and Impact | Research seminar; disseminated research findings at the School of Chemistry |
Year(s) Of Engagement Activity | 2019 |
Description | Panel Member for Early Career Researchers at MICRA/RAMS conferences, Cardiff University |
Form Of Engagement Activity | A formal working group, expert panel or dialogue |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Professional Practitioners |
Results and Impact | Panel member giving advice and input to early career researchers |
Year(s) Of Engagement Activity | 2018 |
Description | Plenary lecture at GDCh JCF Spring Symposium Hanover 2022 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Discussion, questions after talk |
Year(s) Of Engagement Activity | 2022 |
Description | Primary School visit - Nottingham |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Local |
Primary Audience | Schools |
Results and Impact | Gave a talk on chemistry and what I do to Key Stage 2 schoolchildren. |
Year(s) Of Engagement Activity | 2019 |
Description | RSC Sir Geoffrey Wilkinson: An Anniversary celebration |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Postgraduate students |
Results and Impact | Discussion and questions |
Year(s) Of Engagement Activity | 2022 |
Description | RSC delegation member to 11th International Fundamental Science Congress in Putrajaya, Malaysia and a Joint Chemistry Workshop organised by Universiti Putra Malaysia and the Royal Society of Chemistry |
Form Of Engagement Activity | A formal working group, expert panel or dialogue |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Delegation to discuss UK and University of Nottingham Chemistry with academics and students from Malaysia |
Year(s) Of Engagement Activity | 2019 |
Description | School Visit (Gloucester) |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Schools |
Results and Impact | Talk given to schoolchildren on transition metal chemistry, sparking questions and discussion afterwards. |
Year(s) Of Engagement Activity | 2019 |
Description | School visit (Leicester) |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | Regional |
Primary Audience | Schools |
Results and Impact | Talk given to schoolchildren on transition metal chemistry, sparking questions and discussion afterwards. |
Year(s) Of Engagement Activity | 2018 |
Description | School visit (Pontefract) |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Schools |
Results and Impact | Talk given to schoolchildren on transition metal chemistry, sparking questions and discussion afterwards. |
Year(s) Of Engagement Activity | 2018 |
Description | School visit (Sutton Coldfield) |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Schools |
Results and Impact | Talk given to schoolchildren on transition metal chemistry, sparking questions and discussion afterwards. |
Year(s) Of Engagement Activity | 2018 |
Description | Short video for the Science & Innovation Network (SIN Russia) at the British Embassy |
Form Of Engagement Activity | Engagement focused website, blog or social media channel |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Public/other audiences |
Results and Impact | Made a short video on my research and what inspired me to pursue a scientific career. |
Year(s) Of Engagement Activity | 2018 |
Description | Summer School on Catalysis at the Federal University of Sao Carlos, Sao Paolo, Brazil |
Form Of Engagement Activity | Participation in an activity, workshop or similar |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Postgraduate students |
Results and Impact | Delivered a short course on catalysis to students from across Brazil. |
Year(s) Of Engagement Activity | 2020 |
Description | Visit from general public |
Form Of Engagement Activity | Participation in an open day or visit at my research institution |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Public/other audiences |
Results and Impact | International and national members of the general public, meeting with Prof Poliakoff and me, discussion of current research. |
Year(s) Of Engagement Activity | 2018 |