Dr Martin Murray's Research Interests

Current research interests are centred round NMR and phosphorus chemistry. The first uses the 500 MHz spectrometer which is owned by the Molecular Recognition Centre, and projects can involve biological NMR on proteins and peptides. Recent developments in NMR include new 31P-1H correlation experiments. In phosphorus chemistry the two principal areas of activity are polyphosphonates, a joint project with the University of Düsseldorf in Germany, and cyclic phosphorus nitrogen compounds.

New Methods for 31P-1H Correlation Experiments

2-dimensional NMR experiments produce spectra with two frequency axes. Where these are different nuclei (e.g. 1H and 13C) the spectra reveal which proton is coupled to which carbon. The C-H experiment has become common because of its wide application to organic chemistry. In our work with polyphosphorus compounds we require P-H correlation information, so it became necessary to amend the pulse sequence1 to accommodate the different requirements of 31P spectra, such as P-P coupling, the different J values, etc. This work is continuing by extension to inverse spectroscopy (1H and 13C correlation) and 3-dimensional work., and largely involves spectral processing on work-stations.

Chemical and Structural Studies on Polyphosphonates

Polyphosphonic acids and their derivatives are close analogues of polycarboxylates, and have found wide applications in industry. because of their complexation behaviour towards metal ions; this is intimately connected to molecular structure, and the NMR parameters, particularly H-H, H-P, P-P, and C-P couplings provide a rich source of structural information [1]. Their extraction requires use of modern methods of 2D spectroscopy and computer-aided spectral analysis, both of which are being carried out as part of a joint programme, funded by the British Council, with Prof. G.Hägele of the University of Düsseldorf in Germany.

Cyclic Phosphorus Nitrogen Compounds

Although cyclophosphazenes are now compounds of commercial importance as sources of new polymers, much of their basic chemistry has been ignored since first investigated many years ago. 31P NMR provides an excellent means of studying these systems, and we have already applied it to the hydrolysis of P3N3Cl6 and shown that previous assumptions (and recent publications) were erroneous [2]; we have also identified a number of new oxygen bridged bicyclic species. This work, and related work on cyclophosphazanes [3] involves a combination of synthetic chemistry and NMR. All students are trained to operate one of the NMR spectrometers.

  1. G.Hägele, M.Murray, and C.Papadopoulos, Phosphorus, Sulfur, and Silicon, 77, 89-92,(1993)
  2. M.Murray, I.Rillie, and G.Woodward, Phosphorus, Sulfur, and Silicon, 65, 83,(1992).
  3. O.Johnson, G.Woodward, and M.Murray, J.Chem.Soc., Dalton Trans., 1989, 21.
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