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Presenting our research
Dr Simon Duckett01904-432564 e-mail: sbd3@york.ac.uk
Organometallic Chemistry and Reaction Mechanisms Research activities within the group cover a broad range of transition metal chemistry and involves both synthetic and mechanistic projects. The general plan is to
develop new catalysts for alkane functionalisation, harness photochemical methods to generate novel complexes with unusual co-ordination modes, and to study traditional catalytic reactions with a view to improve understanding of how they operate and hence increase their efficiency.
Reactions involving hydrogen: Hydrogen finds a role in many important industrial processes of which hydrogenation, the water gas shift reaction, hydroformylation and acetic acid manufacture are examples. Although these processes are well established there is still a need to optimise the role of the transition metal catalyst if reaction efficiency is to be improved. We have used parahydrogen in conjunction with NMR spectroscopy to follow such reactions with levels of sensitivity that exceed those normally available by over 1000 fold.1,2 Consequently, using this newly developed approach intermediates need no longer be elusive and detailed mechanistic studies are being completed in the group.
Reactions involving C-H activation and alkane functionalisation: While methane is a readily available C1 feedstock its primary use is still as a heat source. Many groups have worked hard to activate C-H bonds with the aim of converting methane into larger structures such as acetic acid. In York we are working on an approach which involves employing two metal centres to activate and functionalise methane. Here the premise is that the first metal centre simply anchors the methyl group, and then the chelate effect allows the second time to functionalise the C-H bond. Recently we have developed a new NMR probe which allows sample to be irradiated by UV light whilst NMR spectra are being recorded.3
Reactions involving Si-H activation: The transition metal mediated formation of new C-Si and Si-Si bonds is used industrially on a very wide scale. While working in this area we have established routes to sila-allyl derivatives involving h3-CH2CHSiMe2 ligands and to metalla-sila-cycles such as M(SiMe2CH2SiMe2). Here the carbo-cyclic analogues, allyl complexes, find widespread use organometallic chemistry as reagents for organic synthesis. Furthermore, you will be familiar with the idea that C-C bond formation can be achieved by ring opening polymerisation via metallacyclobutane intermediates. We have therefore been actively developing the co-ordination chemistry of these ligands, prepared by photochemical Si-H bond activation, and in-situ-functionalisation of reactive Si-Cl bonds, as a prelude to extending their use into catalytic chemistry.
Our work provides excellent opportunities for developing skills in inorganic and organometallic synthetic techniques. These will include the use of Schlenk lines, high vacuum lines, photochemical cells, and inert atmosphere gloveboxes. Physical techniques such as IR, HPLC, GC, UV, mass spec and NMR are employed to monitor reactions and characterise products. The group has a particularly strong interest in NMR, having access to its own dedicated 400 MHz spectrometer. In addition it has 50 % of the time on a 400 MHz spectrometer equipped for in situ photochemistry and a 500 MHz instrument with a cryo-probe.
Selected Publications: Duckett, S. B. and Blazina, D, The study of inorganic systems by NMR spectroscopy in conjunction with parahydrogen induced polarisation. Eur. J. Inorg. Chem. 2003,
2901-2912. Blazina, D, Duckett, S. B., Dyson, P. J. and Lohman, J. A. B. Hydrogenation Catalysis by Triruthenium Clusters: A Mechanistic Study Using Parahydrogen Induced
Polarization. Chemistry a European Journal. 2003, 9, 1045-1061. Godard, C., Callaghan P., Cunningham J. L., Duckett S. B., Lohman J. A. B. and Perutz R. N. NMR characterisation of unstable solvent and dihydride complexes
generated at low temperature by in-situ UV irradiation. Chemical Communications, 2002, 2836-2837.
Group Publications List Group Photographs Visit Simon Duckett's Group website Back to staff page Back to PhD studentship vacancies page Last updated: 30 March 2003 © Department of Chemistry, University of York.
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