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Approches de complexes carbéniques hétérosubstitués originaux

Abstract : Carbenic complexes have received great attention over the last past 15 years. The first part of this manuscript is a general introduction about theses complexes. First used as stoichiometric reagents in organic syntesis, carbenic complexes have become powerful catalysts thanks to the development of stable carbenes. Different approaches are then proposed for the synthesis of original heterosubstituted carbenic complexes.
In the second part, the synthesis and coordination chemistry of aminoarylcarbenes featuring a biphenyl or binaphtyl backbone are described. The geometry of the biphenyl moiety in the ensuing complexes is found to be different to those encountered in the analogous biphenylphosphine complexes. It appears to be related to the hybridization , sp2vs. sp3, of the donating group (carbene or phosphine). This peculiar geometry of the biphenyl backbone induces different and new coordination behaviour compared to those found in biphenylphosphine complexes.
The third part deals with the synthesis of aminocarbene/phosphine complexes by insertion of a
metal fragment into the P-C bond of C-aminoylides. In a case of cyclic C-aminoylides based on a biphenyl backbone, this methodology allows the synthesis of heteroditopic aminocarbene/phosphine, analogs to the well known BIPHEP and BINAP complexes.
The synthesis and coordination properties of some diazophosphines are described in the fourth part. diazodiphosphine complexes are not stable and rearrange into C-chloro diphosphinomethanides. An experimental and theoretical study of the dissociation of C-pyridinodiphosphinomethanides shows the transient formation of palladadiphosphinocarbenes. In addition, DFT calculations reveal a distorted geometry associated with an original inverted electronic configuration for these singlet metalladiphosphinocarbenes and exibit unusal transannular PdC interactions (C PD donation and Pd M back - donation).
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Submitted on : Tuesday, January 15, 2008 - 1:21:18 PM
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  • HAL Id : tel-00192093, version 1



J. Vignolle. Approches de complexes carbéniques hétérosubstitués originaux. Autre. Université Paul Sabatier - Toulouse III, 2006. Français. ⟨tel-00192093⟩



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