Contact: Duncan Carmichael
Phosphorus centres that respond to external stimulate: redox- switchable properties.
The first examples of phosphametallocene complexes contaning ruthenium, cobalt, rhodium,  iridium, and nickel were all prepared in the laboratory. Extensive studies of these compounds have shown that the presence of the phosphorus atom causes only a relatively minor electronic perturbation In monophospholyl substituted ligands, and that the phosphametallocene products show recognisable 'metallocene- type' character, both with respect to magnetic and redox properties.
Such phosphametallocenes provide a framework in which the phosphorus atom can undergo unusual redox chemistry. More classical phosphine ligands whose behaviour can be switched quite emphatically through redox chemistry have also been studied within a consortium led by Dr Feréderic Paul the Université de Rennes 1.[5a] in these ligands, a chemically reversible oxidation of the redox sensitive organoiron end group leads to a dimerisation process that has the effect of eliminating the phosphorus lone pair. The coordination chemistry of these redox- switchable ligands has also been studied.
 D. Carmichael, L. Ricard, F. Mathey, Journal of the Chemical Society-Chemical Communications 1994, 1167-1168. Link
 K. Forissier, L. Ricard, D. Carmichael, F. Mathey, Organometallics 2000, 19, 954-956. Link
 C. Burney, D. Carmichael, K. Forissier, J. C. Green, F. Mathey, L. Ricard, Chemistry-a European Journal 2003, 9, 2567-2573. Link
 C. Burney, D. Carmichael, K. Forissier, J. C. Green, F. Mathey, L. Ricard, Chemistry-a European Journal 2005, 11, 5381-5390. Link
 a): D. Carmichael, G. Goldet, J. Klankermayer, L. Ricard, N. Seeboth, M. Stankevic, Chemistry-a European Journal 2007, 13, 5492-5502 Link; b): D. Carmichael, J. Klankermayer, E. Muller, K. M. Pietrusiewicz, L. Ricard, N. Seeboth, S. Sowa, M. Stankevic, Organometallics 2011, 30, 1804-1811. Link