New ligand systems for metal-based catalysis: Synthesis, screening and theoretical studies
Lead Research Organisation:
University of East Anglia
Department Name: Chemistry
Abstract
There is currently substantial growth in the petrochemical industry in the Far East. This is particularly the case for the Chinese Petrochemical Industry. As a consequence, there is also currently a great deal of academic interest in the field in that part of the world, with various groups actively engaged in the development of new catalytic systems. This is in stark contrast to the situation in the UK, which has been stagnent for some time, with much of the industry moving to mainland Europe or the States, with an inevitable negative knock on effect for UK academia. Interestingly however, there are now signs of a recovery, reflected in the fact that Dalton Transactions are about to publish a special issue later this year on olefin polymerisation. It is against this background that we feel well-placed to maintain the UKs academic interest in the development of new catalysts for olefin polymerisation (and ring opening polymerisations). Our experimental studies on catalyst development are on-going with the groups of Profs Sun (Beijing) and Yamato (Saga), complemented by the theoretical studies conducted by the Kasai group in Osaka. Other groups in mainland China (Changchun), Hong Kong (City U and HKUST) and Japan (Kumamoto) are now keen to join the project.A related area of chemistry is to utilise calixarene assemblies as nanopots for organic catalysis (and prehaps also polymerisation catalysis). This includes generation of a red/ox potential by absorption of photons by semiconductor Quantum Dots. Calixarenes will be bound in close proximity to the QDs' surface. Small organic 'guest'-molecules will enter the calixarene cavity and be transformed. The activation energy (electrochemical reduction potential) will be reduced as compared with 'direct' reduction by entropic profit of the binding of the reactants at the calixarene. This project will bring on board added expertise from the PIs own institution, with results guided by modelling performed in Osaka.Finally, peptidocalixarene frameworks will be used to mimic the secondary interactions found in the active site of all iron hydrogenase. Calculations performed in Osaka suggets that a calix[5]arene platform is best suited to provide the requisite iron - iron separation, and synthetic work will be conducted at UEA, guided by the theoretical studies in Osaka.
Planned Impact
The planned projects will benefit the partner research groups and their respective parent institutions, and the international chemistry community in general through the dissemination of the results. Indeed, impact of research results will be maximised via peer-reviewed scientific journals, conference presentations, editorials, focus articles and, if appropriate, through the general media. The programme will be impacted directly by deepening collaboration between the PI and the Far East participants. All groups will be in weekly e-mail contact to maintain progress and momentum, and a number of workshop-style symposia will be held when the PI is in the Far East, where upon Chinese/Japanese students will be encourage to read/present their work in english. Such workshops and also seminars given by the PI may well prove to be useful recruiting tools, whereby the overseas researchers bring their fellowships and scholarships to UK institutions. Furthermore, UK researchers may also wish to take up their fellowships in China/Hong Kong/Japan, and the PI will be ideally placed to broker such 'deals'. The exchange of researchers between the UK and China/Hong Kong/Japan will offer new cultural experiences for those involved, leading to better cross-cultural understanding and a positive impact on UK/China/Hong Kong/Japan relations. Contrasting research styles and personalities will lead to intellectual and creative challenges which can only serve to enhance the research environment. Integration of the research themes will greatly improve productivity and quality of the research output, since the combined expertise of the research teams is far greater than the sum total of the participating groups acting alone. Plastic materials are essential in our every day life and find use in almost all domestic and industrial appliances. Low density, low cost, combined with high versatility have made such materials ideal substitutes for ferrous and non-ferrous metallic materials. Commodity polymers are used in packaging, clothing, car manufacturing, etc. Specialty polymers find use in electronics, bullet-proof vests, modern aircrafts, and the list goes on. The consumption of plastics is mainly driven by the food and packaging sector which, for the UK, represents 38 % of the annual plastic consumption. Our catalytic studies are ultimately aimed at providing new, low-cost routes to plastic materials and the availability of new biodegradable polymers with desirable properties would impact on everyday life. This is particularly topical given the current problems with landfill sites, which is an increasingly worrying issue in the UK (and elsewhere).
Organisations
People |
ORCID iD |
| Carl Redshaw (Principal Investigator) |
Publications
Zhou Z
(2012)
Synthesis, structure and photophysical properties of 2-benzhydryl-4-methyl-6-(aryliminomethyl)phenol ligands and the zinc complexes thereof
in Inorganica Chimica Acta
Zhou Z
(2012)
Nickel bis{4,6-dibenzhydryl-2-[(arylimino)methyl]phenoxylate} complexes: Synthesis, structures, and catalytic behaviour towards ethylene and norbornene
in Catalysis Science & Technology
Zhou Z
(2012)
6-Benzhydryl-4-methyl-2-(1H-benzoimidazol-2-yl)phenol ligands and their zinc complexes: Syntheses, characterization and photoluminescence behavior
in Inorganica Chimica Acta
Zhang W
(2012)
Dimethylaluminium aldiminophenolates: synthesis, characterization and ring-opening polymerization behavior towards lactides.
in Dalton transactions (Cambridge, England : 2003)
Zhang W
(2012)
Trimetallic yttrium N-(2-methylquinolin-8-yl)benzamides: synthesis, structure and use in ring-opening polymerization (ROP) of e-caprolactone
in New Journal of Chemistry
Zhang W
(2011)
2-(N-Alkylcarboxamide)-6-iminopyridyl palladium and nickel complexes: coordination chemistry and catalysis.
in Dalton transactions (Cambridge, England : 2003)
Zhang W
(2012)
2-Aldiminophenoxytitanium chloride complexes: Synthesis, characterization, and ethylene (co-)polymerization behavior
in Journal of Organometallic Chemistry
Zhang W
(2011)
Synthesis and Characterization of Dialkylaluminum Amidates and Their Ring-Opening Polymerization of e-Caprolactone
in Organometallics
Yu J
(2011)
2-[1-(2,6-Dibenzhydryl-4-methylphenylimino)ethyl]-6-[1-(arylimino)ethyl]pyridylcobalt(II) dichlorides: synthesis, characterization and ethylene polymerization behavior.
in Dalton transactions (Cambridge, England : 2003)
Sun WH
(2012)
Ethylene polymerization by 2-iminopyridylnickel halide complexes: synthesis, characterization and catalytic influence of the benzhydryl group.
in Dalton transactions (Cambridge, England : 2003)
Sun WH
(2011)
Methylaluminium 8-quinolinolates: synthesis, characterization and use in ring-opening polymerization (ROP) of e-caprolactone.
in Dalton transactions (Cambridge, England : 2003)
Sun W
(2012)
2-(1-(Arylimino)ethyl)-8-arylimino-5,6,7-trihydroquinolylcobalt dichloride: Synthesis and polyethylene wax formation
in Applied Catalysis A: General
Sun W
(2012)
Enhancing the Activity and Thermal Stability of Iron Precatalysts Using 2-(1-{2,6-bis[bis(4-fluorophenyl)methyl]-4-methylphenylimino}ethyl)-6-[1-(arylimino)ethyl]pyridines
in Macromolecular Chemistry and Physics
Song S
(2011)
Synthesis, characterization and ethylene oligomerization behaviour of 8-(1-aryliminoethylidene)quinaldinylnickel dihalides
in Catalysis Science & Technology
Song S
(2011)
Iron(II) and cobalt(II) complexes bearing 8-(1-aryliminoethylidene) quinaldines: Synthesis, characterization and ethylene dimerization behavior
in Journal of Organometallic Chemistry
Song S
(2011)
Synthesis, characterization and catalytic behavior toward ethylene of cobalt(II) and iron(II) complexes bearing 2-(1-aryliminoethylidene)quinolines
in Journal of Organometallic Chemistry
Song S
(2011)
2-(1-Aryliminoethylidene)quinolylnickel(II) dibromides: Synthesis, characterization and ethylene dimerization capability
in Journal of Organometallic Chemistry
Song S
(2012)
2-(1-Arylimino)quinolylnickel halides: Synthesis, characterization and catalytic behavior towards ethylene
in Journal of Organometallic Chemistry
Shen M
(2010)
Synthesis and characterisation of alkylaluminium benzimidazolates and their use in the ring-opening polymerisation of e-caprolactone.
in Dalton transactions (Cambridge, England : 2003)
Ruan Q
(2018)
A three-dimensional (time, wavelength and intensity) functioning fluorescent probe for the selective recognition/discrimination of Cu2+, Hg2+, Fe3+ and F- ions.
in Dalton transactions (Cambridge, England : 2003)
Redshaw C
(2011)
Ethylene Polymerization Catalysis by Vanadium-Based Systems Bearing Sulfur-Bridged Calixarenes
in Organometallics
Redshaw C
(2012)
Cellular uptake of a fluorescent vanadyl sulfonylcalix[4]arene.
in Chemical communications (Cambridge, England)
Ni XL
(2012)
Hexahomotrioxacalix[3]arene derivatives as ionophores for molecular recognition of dopamine, serotonin and phenylethylamine.
in Organic & biomolecular chemistry
Ni XL
(2011)
Novel ion-pair receptors based on hexahomotrioxacalix[3]arene derivatives.
in Organic & biomolecular chemistry
Nandre JP
(2017)
A chemosensor for micro- to nano-molar detection of Ag+ and Hg2+ ions in pure aqueous media and its applications in cell imaging.
in Dalton transactions (Cambridge, England : 2003)
Liu H
(2012)
Synthesis, characterization and ethylenepolymerization behavior of nickel dihalide complexes bearing bulky unsymmetrical a-diimine ligands
in Catal. Sci. Technol.
Liu H
(2011)
Synthesis, characterization and ethylene oligomerization behavior of 2-benzoimidazol-8-ethoxyquinolylnickel dihalides.
in Dalton transactions (Cambridge, England : 2003)
Jiang XK
(2018)
A Hexahomotrioxacalix[3]arene-Based Ditopic Receptor for Alkylammonium Ions Controlled by Ag? Ions.
in Molecules (Basel, Switzerland)
Huang W
(2011)
2-(1-(Arylimino)propyl)quinolin-8-olate half-titanocene dichlorides: synthesis, characterization and ethylene (co-)polymerization behaviour.
in Dalton transactions (Cambridge, England : 2003)
Huang W
(2011)
Synthesis, characterization and ethylene (co-)polymerization behavior of half-titanocene 2-(1-(arylimino)ethyl)quinolin-8-olate chlorides
in Catalysis Science & Technology
Huang W
(2012)
Synthesis, characterization, and the ethylene (co-)polymerization behaviour of half-titanocene dichloride 2-aryliminoquinolin-8-olates
in Catalysis Science & Technology
Hou X
(2012)
N-(5,6,7-trihydroquinolin-8-ylidene)-2-benzhydrylbenzenaminonickel halide complexes: synthesis, characterization and catalytic behavior towards ethylene polymerization.
in Dalton transactions (Cambridge, England : 2003)
He F
(2012)
2-[1-(2,6-dibenzhydryl-4-chlorophenylimino)ethyl]-6-[1-aryliminoethyl]pyridyl cobalt dichlorides: Synthesis, characterization and ethylene polymerization behavior
in Journal of Organometallic Chemistry
Chai W
(2012)
Synthesis, characterization and ethylene oligomerization behavior of N-(2-alkyl-5,6,7-trihydroquinolin-8-ylidene)arylaminonickel(II) dichlorides
in Inorganica Chimica Acta
Ban Q
(2012)
2,6-Dibenzhydryl-N-(2-aryliminoacenaphthylenylidene)-4-chlorobenzenamino-palladium dichlorides: Synthesis, characterization, and use as catalysts in the Heck-reaction
in Journal of Organometallic Chemistry
| 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 |