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Phosphines redox

Contact: Duncan Carmichael 

Phosphorus centres that respond to external stimulate: redox- switchable properties.

The first examples of phosphametallocene complexes contaning ruthenium,[1] cobalt,[2][3] rhodium, [2] iridium,[2] and nickel[4] 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.[5]


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.[6]



[1]        D. Carmichael, L. Ricard, F. Mathey, Journal of the Chemical Society-Chemical Communications 1994, 1167-1168. Link

[2]        K. Forissier, L. Ricard, D. Carmichael, F. Mathey, Organometallics 200019, 954-956. Link


[3]          C. Burney, D. Carmichael, K. Forissier, J. C. Green, F. Mathey, L. Ricard, Chemistry-a European Journal 2003, 9, 2567-2573. Link

[4]          C. Burney, D. Carmichael, K. Forissier, J. C. Green, F. Mathey, L. Ricard, Chemistry-a European Journal  2005, 11, 5381-5390. Link


[5]        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