B.Sc. Adelaide 1995, B.Sc. (Hons) Australian National University 1996, Ph.D. Australian National University 2000.
Senior Lecturer, Deputy Director of Teaching (School of Chemistry), Director of Talented Students Programme (Faculty of Science)
Phone: (02) 9385 4692
Fax: (02) 9385 6141
Room 223, Dalton Building
UNSW, Kensington 2052
Research Group Website
Born 1974. Undergraduate work carried out at the University of Adelaide (B.Sc. 1995) and in The Faculties, Australian National University (B.Sc.(Hons) 1996). Shell Australia Postgraduate Scholar, Research School of Chemistry, Australian National University (Ph.D. 2000). C. J. Martin Postdoctoral Fellow, University Chemical Laboratory, Cambridge (2000-2002). Associate Lecturer, The Open University in East Anglia (2001). Appointed Lecturer 2002 and Senior Lecturer 2007. SSP at Boston College (2009).
Our research falls broadly into the category of physical organic chemistry. However, the areas covered also include biological, bioorganic, synthetic, analytical and environmental chemistry and this demonstrates the range of areas that physical organic chemistry is applicable to. The breadth of topics also illustrates the interdisciplinary nature of the research and the significant scope for collaboration with groups in the more traditional areas of organic chemistry and biochemistry.
The major areas of research are:
Understanding organic processes in ionic liquids
Ionic liquids, also known as room temperature molten salts, are rapidly being developed as an alternative to environmentally harmful organic solvents. However, current understanding of how these solvents affect organic processes is limited and predicting reaction outcomes in these solvents is currently difficult. Our aim is to rectify this situation, by studying well-described processes in these solvents to develop an understanding so that reaction outcomes might be initially rationalised and eventually predicted. We are currently examining a range of substitution and cycloaddition reactions and observing the change in the product outcome and the rate of the processes.
Heteronuclear magnetic resonance spectroscopy
In our efforts to follow reaction kinetics in ionic liquids often the traditional techniques do not function well and as such we have been examining non-traditional methods to follow such reactions. One such technique is to consider NMR spectroscopy of less frequently used nuclei (particularly chlorine-35, bromine-79 and oxygen-17) which offer numerous advantages, particularly in systems in which the more common nuclei in the solvent may interfere with analysis. We are currently investigating the utility of these nuclei and using representative reactions (often linked with the project above) as examples of how the technique might be applied.
Determination of reaction mechanisms
As physical organic chemists, our group also has an interest in developing the understanding of synthetically useful reactions through mechanism elucidation. We have been involved in the determination of the mechanism of bridgehead alkynylation (with Dr Craig Williams, University of Queensland) and novel indole cyclisation processes (with Prof. David Black, UNSW). The latter has led to the investigation of potential new methods to form indole based pentacyclic aromatic structures.
We are also investigating:
- the development of switchable surfaces,
- supramolecular constructs based on carbon frameworks,
- group XIV tetratolyls, and
- the electron donating ability of C-H and C-C bonds.
For more information on all of these research projects, please see the Harper Group Site.
- Yau, H. M.; Keaveney, S. T.; Butler,B. J.; Tanner, E. E. L.; Guerry, Max S.; George, S. R. D.; Dunn, M. H.; Croft, A. K.; Harper, J. B.: "Towards solvent-controlled reactivity in ionic liquids", Pure and Applied Chemistry, accepted January 10th 2013.
- Dunn, M. H.; Cole, M. L.; Harper, J. B.: "Effects of an ionic liquid solvent on the synthesis of γ-butyrolactones by conjugate addition using NHC organocatalysts", RSC Advances 2012, 2, 10160-10162.
- Yau, H. M.; Croft, A. K.; Harper, J. B.: "One-Pot Hammett Plots: A General Method for the Rapid Aquisition of Relative Rate Data", Chemical Communications 2012, 48, 8937-8939.
- Yau, H. M.; Croft, A. K.; Harper, J. B.: "Investigating the origin of entropy-derived rate accelerations in ionic liquids", Faraday Discussions 2012, 154, 365-371.
- Gyton, M. R.; Cole, M. L.; Harper, J. B.: "Ionic liquid effects on Mizoroki-Heck reactions: More than just carbene complex formation", Chemical Communications 2011, 47, 9200-9202.
- George, S. R. D.; Edwards, G. L.; Harper, J. B.: "The effect of ionic liquids on azide-alkyne cycloaddition reactions", Organic and Biomolecular Chemistry 2010, 8, 5354-5358.
- Jones, S. G.; Yau, H. M.; Davies, E.; Hook, J. M.; Youngs, T. G. A.; Harper, J. B.; Croft, A. K.: "Ionic liquids through the looking glass: theory mirrors experiment and provides further insight into aromatic substitution processes", Physical Chemistry Chemical Physics 2010, 12, 1873-1878.
- Yau, H. M.; Howe, A. G.; Hook, J. M.; Croft, A. K.; Harper, J. B.: “Solvent reorganisation as the driving force for rate changes of Menschutkin reactions in an ionic liquid”, Organic and Biomolecular Chemistry 2009, 7, 3572-3575.
- Chan, S. J.; Howe, A. G.; Hook, J. M.; Harper, J. B. : “79Br NMR Spectroscopy as a Practical Tool for Kinetic Analysis”, Magnetic Resonance in Chemistry 2009, 47, 342-347.
- Rosella, C. E.; Harper, J. B. : “The effect of ionic liquids on the outcome of nitrile oxide cycloadditions”, Tetrahedron Letters, 2009, 50, 992-994.
- Yau, H. M.; Barnes, S. A.; Hook, J. M.; Youngs, T. G. A.; Croft, A. K.; Harper, J. B. : "The importance of solvent reorganisation in the effect of an ionic liquid on a unimolecular substitution process", Chemical Communications 2008, 3576-3578.