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Séminaire Chimie ED459

Recent developments in lanthanoid pseudo-Grignard reagent chemistry

Prof. Peter C. Junk (School of Pharmacy & Molecular Sciences, James Cook University, Townsville, Australia)

publié le , mis à jour le

Le Jeudi 14 Février 2013 à 13h45
UM2, salle de cours SC-16.01

We have progressed metal based syntheses using rare earth metals considerably over the past several years. Organo-mercury and -thallium reagents have been extremely versatile reagents in redox transmetallation (equation 1) while the mercury reagents have also found great utility in the more convenient redox transmetallation/protolysis reactions (equation 2).[1] We have now extended this rare earth chemistry to the use of less toxic reagents such as RSnMe3,[2], BiPh3,[3] and most recently using pseudo-Grignard type chemistry[4] (equation 3) and use of I2 to activate the metal (equation 4).[5] This presentation will involve a discussion of the latter two methods.

In lanthanoid pseudo-Grignard chemistry, we have been able to use these reagents in protolysis reactions to deliver heteroleptic iodo(metal organic)lanthanoid species in good yield,[4] despite previous reports of the mixed oxidation state for PhLnI (Ln = Eu, Yb).[5] The species obtained our attempts to crystallise “PhYbI(thf)n” complexes will be presented.

We have recently shown that bulk lanthanoid metal can be activated by a few % of iodine crystals in the presence of a protic ligand to produce metal-organic compounds (equation 4). In this presentation, the new directions of the project will be discussed along with the most recent exciting results.

References :

1. G. B. Deacon et al., J. Organomet. Chem., 647, 50 (2002).
2. S Beaini, G B Deacon, M Hilder, P C Junk and D R Turner, Eur. J. Inorg. Chem., 3434 (2006).
3. M.M. Gillett-Kunnath, J. G. MacLellan, C. M. Forsyth, P.C. Andrews, G. B. Deacon and K. Ruhlandt-Senge, Chem. Commun., 4490 (2008).
4. M Wiecko, G B Deacon and P C Junk, Chem. Commun., 46, 5076 (2010).
5. D. F. Evans et al., J. Chem. Soc. D., 244 (1970) ; J. Chem. Soc. A., 1931 (1971).

Funding for this work provided by The Australian Research Council (DPDP0984775)

Contact local ICGM : Dr. Odile Eisenstein (équipe CTMM)


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