Synthesis, Properties and Reactivity of some Redox-Active Metallophosphines featuring «Fe(dppe)(Cp*)CC» Substituants

Over the two last decades, the design of redox-active molecular structures allowing the control a given property using electron transfer as a stimulus, has constituted an important goal for many researchers, both from the fundamental and applied standpoint.[1] In this context, the synthesis of «metallo-ligands» for which the electronic properties of the coordinating site can be significantly modified upon oxidation or reduction of the appended (organo)metallic site represents an exciting and promising goal, because such compounds open a potential access to a wealth of redox-stimulable molecular assemblies by self-assembling these ligands around various metal centers.[2] We will discuss during this seminar our input in this field through several examples of such metallophosphines, resulting from the coupling of the redox-active «Fe(Cp*)(dppe)CC- » endgroup[3] to various phosphines, as well as, our efforts to characterize the impact of the organometallic redox tag on the coordinating site.

[1] See for instance: (a) P. J. Low, J. Chem. Soc., Dalton Trans., 2005, 2821-2824; (b) F. Paul and C. Lapinte, in Unusual Structures and Physical Properties in Organometallic Chemistry, eds. M. Gielen, R. Willem and B. Wrackmeyer, Wiley, San-Francisco, 2002, pp. 219-295; (c) O. R. Luca, R. H. Crabtree, Chem. Soc. Rev., 2013, 42, 1440; (d) F. Miomandre, J. F. Audibert, Q. Zhou, P. Audebert, P. Martin and J. C. Lacroix, Electrochim. Acta 2013, 110, 56-62; (e) G. Grelaud, M. P. Cifuentes, F. Paul and M. G. Humphrey, J. Organomet. Chem., 2014, 751, 181-200.
[2] J. Lehn, Supramolecular Chemistry: Concepts and Perspectives, VCH, Weinheim, 1995.
[3] F. Paul and C. Lapinte, Coord. Chem. Rev., 1998, 178/180, 431-509.
[4] (a) F. Paul, S. Goeb, F. Justaud, G. Argouarch, L. Toupet, R. F. Ziessel and C. Lapinte, Inorg. Chem., 2007, 46, 9036-9038; (b) A. Tohmé, G. Grelaud, G. Argouarch, T. Roisnel, A. Bondon, F. Paul Inorg. Chem. 2013, 52, 8993; (c) A. Tohmé, G. Grelaud, G. Argouarch, T. Roisnel, S. Labouille, D. Carmichael, F. Paul, Angew. Chem. Int. Ed., 2013, 52, 4445.