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Nouveaux ligands donneurs mixtes contenant un atome de phosphore sp2.

Abstract : The work presented here brings together the results on the preparation of phosphamétallocènes mainly around M = Ru. A better understanding of phenomena governing the coordination of transition metals on soft anions phospholures and preparation of phospholures modified by ester group allowed us to promote the coordination mode of 5 and solve the chirality by simple crystallization. We showed that this synthesis method of resolution is quite general and apply in those cases where M = Fe, Ru, and Mn. Taking into account specific issues related to the development of an ester unresponsive on a skeleton sensitive to oxidation, methods for preparing enantiopure phospamétallocènes have been developed. With access to the four oxidation states alkyl alcohol / carbocation, aldehyde, acid carbon centered on position 2 cycle phospholyle many derivatives can be easily prepared. To enhance the modularity of the skeleton is important for the development of asymmetric catalysts, the variation of four settings (the central metal, phosphine, phosphorus bridge linking the chelate, secondary substituent in position 5) gave rise to several families ligands. These ligands have been evaluated on the test reaction of hydrogenation of a-acétamidocinnamates and enantiomeric excesses are better with than with phospharuthénocènes phosphaferrocènes tested. The dependence of excess and with different external parameters (temperature) or specific ligands (replacing the bridge, the central metal, phosphine ...) has been studied.
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Submitted on : Thursday, July 29, 2010 - 2:01:30 PM
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  • HAL Id : pastel-00002310, version 1



Nicolas Seeboth. Nouveaux ligands donneurs mixtes contenant un atome de phosphore sp2.. Chimie. Ecole Polytechnique X, 2005. Français. ⟨pastel-00002310⟩



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