Modelling chemical exchange reactions in Transition Metal-Phosphine Complexes

Friday 21 March 2008

The STFC e-Science HPCSG group run the computing and storage infrastructure for the EPSRC National Service for Computational Chemistry Software (NSCCS).

Professor Stuart Macgregor (link opens in a new window) of Heriot-Watt University has used the computing resources of the NSCCS to computationally model ligand substitution reactions of organometallic complexes. Organometallic compounds offer broad scope for the design of anti-cancer agents where the control of ligand substitution is key to attacking the DNA target while not damaging other sites.

Phosphine ligands, are ubiquitous as ligands in transition metal (TM) homogeneous catalysis. The phosphine ligand plays a crucial role in controlling activity, but it is essential that it remains an innocent 'spectator' and does not itself undergo reaction. Decomposition of TM-phosphine complexes is, however, a well-known problem. Prof Macgregor considered two general mechanisms for F/Ph exchange which differ only in the order of group transfer between the metal and the participating phosphorus centre. The reaction profiles for exchange, and the barriers to exchange along both pathways were computed.

This work was performed in collaboration with Dr. Vladimir V. Grushin and colleagues at the Central Research and Development, E. I. Dupont de Nemours and Company.

A detailed account of this research is available in the 13th edition of the NSCCS newsletter (link opens in a new window).