Utilising the Coordination chemistry tool-box to tackle issues ranging from Catalysis to Cancer

Lead Research Organisation: University of Hull
Department Name: Physical Sciences

Abstract

We are bringing together internationally recognised laboratories to collaborate on projects which will advance UK global scientific interactions with key partners, China and Japan. The broad areas of science in which the laboratories will engage are polymerization catalysis, energy and cancer chemistry. The UK partner has a high profile in coordination chemistry, and the partnerships with the groups in the Far East will enable access to state-of-the-art facilities which are not readily available in the UK.
The partnerships will
i) design new catalysts capable of forming plastic materials with new properties. With a view to the current landfill problems, we will also focus on the formation of biodegradable polymers.
ii) probe how the molecular structure of metal organic frameworks (compounds adopting grid-like 3D structures) influence the storage capacity for gases such as hydrogen and carbon dioxide.
iii) design new catalysts for spliting water or conducting cataysis in confined spaces; such systems will use abundant metals rather than precious metals.
iv) investigate metal-based compounds with a view to identifying new anti-cancer agents.
Much of the synthetic work will be guided by molecular modelling conducted in Japan.

Planned Impact

The programme will be impacted directly by deepening collaboration between the PI and the Far East Participants. Seminars/workshops involving the PI will prove to be useful recruitment tools, whereby overseas researchers bring their fellowships/scholarships to the UK. Furthermore, UK researchers may also wish to take up fellowships in China/Japan, and the PI will be ideally placed to broker such 'deals'. The exchange of researchers between the UK and the Far East will offer new cultural experiences for those involved, leading to better cross-cultural understanding and a positive impact on UK/China/Japan relations.
Each research theme will have impact: For the water splitting and gas storage projects, i) the synthesis of synthetic complexes based on abundant materials capable of electrocatalysis/H2 generation will be a major step forward, and will offer exciting new and/or improved prospects for useful fuel materials. ii) The safe and convenient storage of hydrogen is fundamental to a hydrogen economy. The strategic implications of research on alternative hydrogen storage materials have been realized by a number of countries and the USA in-particular have set a number of short-term goals to minimize weight and volume for on-board storage. The successful development of such fuel cell powered vehicles would result in significant reductions in CO2 emissions, and perhaps more importantly will help solve the impending worldwide fuel crisis facing mankind later this century.
For the polymerization catalysis projects: Our catalytic studies are mainly aimed at providing new, low-cost routes to useful plastic materials as well as other sides produces such as waxes. Furthermore, the availability of new biodegradable polymers with desirable properties would impact on everyday life. This is topical given the current issues with landfill sites, which are an increasingly worrying issue both in the UK and the Far East.
The metal-based anti-Cancer work involves development of therapeutic pharmaceuticals that ensure a localised effect is targeted to a specific organ or indeed cell type. For the patient, this can give reduced side effects and fewer visits for treatment, adding to the quality of their life.
Industries in both the UK and Far East will also benefit from new highly skilled personnel trained via these multidisciplinary projects.
Academics: The planned projects will benefit the Hull, Chinese and Japanese research groups, and the international chemistry community in general through dissemination of the results. Impact of research results will be maximized via peer-reviewed in leading international journals (eg Angew Chemie, JACS, Chem Commun., Organometallics) and ii) presented at national (RSC) and international conferences (ACS). This will be supplemented by editorials, focus articles and, if appropriate, through the general media.
Exploitation and application
Hull has in place arrangements with the Far East partners for the exploitation of research, and any formal agreement to exploit for profit the results generated in this project would be negotiated through that office; the PI has experience with patenting/commercialisation of research results.

Publications

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Al-Khafaji Y (2015) Tetraphenolate niobium and tantalum complexes for the ring opening polymerization of e-caprolactone. in Dalton transactions (Cambridge, England : 2003)

 
Description A number of new catalysts have been discovered which can produce polymers at high temperatures and are therefore suitable for use under industrial conditions. We have also produced a number of new catalysts with high efficient for producing biodegradable polymers.
Exploitation Route Because these catalysts generate new IP there is the possibility that new (and old) polyolefin companies can use these systems rather than buy our licences rather than purchase told and expensive catalyst technology.
Sectors Chemicals

URL http://my.rsc.org/blogs/74/834
 
Description At this stage, the work has been cited in the scientific literature by researchers around the world. It has yet to reach a stage where any pilot plants are using this technology.
First Year Of Impact 2014
Sector Chemicals
Impact Types Economic

 
Description Borealis 
Organisation Borealis
Country Austria 
Sector Private 
PI Contribution The Hull lab prepares and characterises new pre-catalysts, which are then sent to Finland.
Collaborator Contribution The complexes supplied by Hull are screened under industrial conditions for olefin polymerization/co-polymerization.
Impact Highly active, thermally stable, ethylene polymerization pre-catalysts based on Niobium and Tantalum imine systems. C. Redshaw, M. Walton, L. Clowes, D. L. Hughes, A.-M. Fuller, Y. Chao, A. Walton, V. Sumerin, P. Elo, I. Soshnikov, W. Zhao and W.-H. Sun. Chem. Eur. J. 2013, 19, 8884-8899. Vanadium(III) phenoxyimine complexes for ethylene or epsilon-caprolactone polymerization: mononuclear versus binuclear pre-catalysts. L. Clowes, M. Walton, C. Redshaw, Y. Chao, A. Walton, P. Elo, V. Sumerin and D. L. Hughes. Cat. Sci. & Tech. 2013, 3, 152-160.
Start Year 2011
 
Description NWU 
Organisation North-West University
Country South Africa 
Sector Academic/University 
PI Contribution Set up a lab at Northwest University (NWU) in Xi'an
Collaborator Contribution NWU has provided a masters student and monies for equipment.
Impact Metallocalixarene catalysts: ?-olefin polymerisation and ROP of cyclic esters. C. Redshaw, Dalton Trans. 2016, 45, 9018 - 9030.
Start Year 2016
 
Description SNU 
Organisation Sichuan Normal University
Country China 
Sector Academic/University 
PI Contribution Set up a lab at Sichuan Normal University (SNU). Four students graduated with a masters degree. CR spend 3 months each year (for 4 years) running the lab.
Collaborator Contribution SNU selected the students who spoke reasonable English. SNU also provide the research funding to run the lab.
Impact Organoaluminium complexes derived from Anilines or Schiff bases for ring opening polymerization of epsilon-caprolactone, delta-valerolactone and rac-lactide. X. Wang, K. -Q. Zhao, S. Mo, Y. Al-Khafaji, T. J. Prior, M. R. J. Elsegood and C. Redshaw, submitted to Eur. J. Inorg. Chem. DOI: 10.1002/ejic.201601415 Structure and emission studies of Schiff-base [2+2] macrocycles derived from 2,2/-oxydianiline and the ROP capability of their organoaluminium complexes. W. Yang, K.-Q. Zhao, T. J. Prior, D. L. Hughes, A. Arbaoui, T. Bian, Y. Chao, M. R. J. Elsegood and C. Redshaw, Dalton Trans. 2016, 45, 11990-12005. Manganese coordination chemistry of bis(imino)phenoxide derived [2 + 2] Schiff-base macrocyclic ligands. W. Yang, K. -Q. Zhao, B. -Q. Wang, C. Redshaw, M. R. J. Elsegood, J. -L. Zhao and T. Yamato, Dalton Trans. 2016, 45, 226-236. Molybdenum complexes derived from the oxydianiline [(2-NH2C6H4)2O]: Synthesis, characterization and ?-caprolactone ROP capability. W. Yang, Q. -K. Zhao, C. Redshaw, and M. R. J. Elsegood, Dalton Trans, 2015, 44, 13133-13140. Para-Selective C-H Amidation of Simple Arenes with Nitriles as the Amino Source. S.-K. Xiang, J.-M. Li, H. Heung, C. Feng, H.-L. Ni, X.-Z. Chen, B.-Q. Wang, K. -Q. Zhao, P. Hu and C. Redshaw Advanced Synthesis and Catalysis, 2015, 357, 3435-3440. Vanadyl complexes bearing bi-dentate phenoxyimine ligands: Synthesis, structural studies and ethylene polymerization capability. J. Ma, K.-Q. Zhao, M. Walton, J. A. Wright, J. W.A. Frese, M.R.J. Elsegood, Q. Xing, W.-H. Sun and C. Redshaw. Dalton Trans. 2014, 43, 8300-8310. Ethyleneglycol Tungsten Complexes of calix[6 and 8]arenes: Synthesis, Characterization and ROP of ?-caprolactone. Y. Li, K.-Q. Zhao, C. Feng, M. R.J. Elsegood, T. J. Prior, X. Sun, and C. Redshaw, Dalton Trans. 2014, 43, 13612-13619. Organoaluminium complexes of o-,m-,p-anisidines: Synthesis, structural studies and ROP of ?-caprolactone. Y. Li, K.-Q. Zhao, M. R.J. Elsegood, T. J. Prior, X. Sun, S. Mo and C. Redshaw, Cat. Sci & Tech., 2014, 4, 3025-3031. A convenient tandem one-pot synthesis of donor-acceptor-type triphenylene 2,3-dicarboxylic esters from diarylacetylene. C. Feng, X.-L. Tian, J. Zhou, S.-K, Xiang, W.-H. Yu, B.-Q. Wang, P. Hu, C. Redshaw and K.-Q. Zhao, Org. Biomol Chem. 2014, 12, 6977-6981. Tri- and tetra-dentate imine vanadyl complexes: Synthesis, structure and ethylene polymerization/ring opening polymerization capability. J. Ma, K.-Q. Zhao, M. J. Walton, J. A. Wright, D. L. Hughes, M. R.J. Elsegood, K. Michiue, X. Sun and C. Redshaw, Dalton Trans. 2014, 43, 16698-16706. Selective ethylene trimerization by titanium complexes bearing phenoxy-imine ligands with a pendant arm: NMR? and EPR?spectroscopic studies of the reaction intermediates. J. Ma, K.-Q. Zhao, I. E. Soshnikov, N. V. Semikolenova, V. A. Zakharov, K. P. Bryliakov, C. Redshaw and E. P. Talsi, Organometallics, 2014, 33, 1431-1439. Bi- and tri-dentate imino-based iron & cobalt complex pre-catalysts for ethylene oligo-/polymerization. J. Ma, C. Feng, S. Wang, K.-Q. Zhao, W.-H. Sun , C. Redshaw and G.A. Solan, Inorg. Chem. Frontiers, 2014, 1, 14-34 (Front cover for the first issue of the first volume). Tetraphenylene-Triphenylene Oligomers with an Aggregation-induced Emission effect and Discotic Columnar Mesophase. W.-H. Yu, C. Chen, B.-Q. Wang, C. Redshaw and K.-Q. Zhao, RSC Advances, 2013, 3, 14099-14105. Synthesis of Triphenylene Discotic Liquid Crystals Possessing Nine Alkyl Chains: Influence of Molecular Symmetry and Chain Length on Mesomorphism. L. Xiao, H. Wang, C. Redshaw, Q.-K. Zhao. Molecular Crystals and Liquid Crystals. 2013, 577, 25-35. Mono-Disperse Triphenylene Discotic Liquid Crystal Oligomers synthesized by Click Chemistry. Y.-F. Bai, K.-Q. Zhao, P. Hu, B.-Q. Wang and C. Redshaw, Curr. Org. Chem. 2013, 17, 871 - 885. Copper-free click chemistry between azides and internal alkynes for triphenylene discotic liquid crystal trimer formation. Y. -F. Bai, L. Bao, P. Hu, B. -Q. Wang, C. Redshaw and K.-Q. Zhao, Liquid Crystals 2013, 40, 97 - 105.
Start Year 2012
 
Description V cats 
Organisation Mitsui Group
Country Japan 
Sector Private 
PI Contribution Complex pre-catalysts are made in the Hull Redshaw lab and then sent to Japan for evaluation.
Collaborator Contribution Mitsui Chemical Corporation screen the complexes for their ability to polymerize alpha olefins and co-polymerize alpha olefins under robust industrial conditions.
Impact Tri- and tetra-dentate imine vanadyl complexes: Synthesis, structure and ethylene polymerization/ring opening polymerization capability. J. Ma, K.-Q. Zhao, M. J. Walton, J. A. Wright, D. L. Hughes, M. R.J. Elsegood, K. Michiue, X. Sun and C. Redshaw, Dalton Trans. 2014, 43, 16698-16706.
 
Title NIOB AND TANTAL COMPLEXES AS CATALYSTS FOR OLEFIN POLYMERIZATION 
Description This invention relates to complexes formed by the combination of a metal (M) and various ligands (L). The metals (M) include niobium and tantalum. The complexes serve to catalyze the polymerization of hydrocarbons. The process comprises mixing the complex or a combination of the complexes with a co-catalyst and one or more monomers. 
IP Reference WO2014135824 
Protection Patent granted
Year Protection Granted 2014
Licensed No
Impact High impact publication in Chemistry A European Journal.
 
Description Beijing 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Schools
Results and Impact We had a stall at the Beijing Science festival and the PI talked to school kids and their parents about UK science and chemistry at Hull in particular. There were around 25,000 attendees.

This greatly raised the profile of Hull and the UK. Other countries were present and so it was vital for the UK to also be present.
Year(s) Of Engagement Activity 2014
 
Description Plenary 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Participants in your research and patient groups
Results and Impact Redshaw gave a Plenary lecture in Beijing at the conference on high technology polymers.

This was attended by scientists from around the globe and therefore raised the profile of the materials research at Hull and in the UK.
Year(s) Of Engagement Activity 2014