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Spins under pressure: A mechanistic understanding of homogeneous catalysis by high pressure EPR.

15 January 2013

A £498K grant has been awarded to Dr. Damien Murphy by EPSRC to develop a high pressure Electron Paramagnetic Resonance system in the School of Chemistry.

Spins under pressure: A mechanistic understanding of homogeneous catalysis by high pressure EPR.

A 4 year research project in high pressure Electron Paramagnetic Resonance spectroscopy (HP-EPR) has been awarded to Dr. Damien Murphy by EPSRC (EP/K017322/1: £498K) to study the mechanistic pathways involved in catalytic reactions. As part of the CCI facilities, a new X-band CW EPR spectrometer will be used to develop and test the high pressure cell for air-sensitive systems; later the cell will be adapted for applications in pulsed EPR mode, in order to study catalytic reactions under extreme conditions. Because pressure is a primary thermodynamic parameter of central importance in reaction kinetics, chemical equilibria, molecular conformations and molecular interactions, it is very important in catalysis, and becomes a crucial and available parameter to study the reaction mechanisms. Since the equilibria, selectivity, population of states, conformations of the catalyst - substrate intermediates and role of solvent interactions, can all be affected, HP-EPR will be used to examine these properties. The structure, redox states, electronic and spin states, dynamics, non-covalent interactions, conformation changes and relaxation behaviour, can all be analysed by these advanced HP-EPR techniques, using the high pressure facility as a means of controlling and enhancing mechanistic variables in order to facilitate their investigations. Pressure also influences the outcome of most chemical processes, and therefore the HP-EPR facility developed in this project can also be applied to a range of other problems in chemistry involving free radicals, from organic and inorganic reactions, to electron transfer and activation of small molecules. Specific collaborative studies in heterogeneous catalysis, spin crossover phenomena, and electron spin states in condensed media, will also be investigated during the project.

Further information on the EPR/ENDOR group: http://www.cardiff.ac.uk/chemy/epr/