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Synthèse et caractérisation de phosphine, borane, amine sur plateforme ferrocène polyfonctionnelle

Abstract : Ferrocene platforms are useful in coordination chemistry and catalysis thanks to their robustness and versatile functionalization. Ferrocene backbone allows the implantation of several key functional groups in a restricted space, inducing close proximity and potential polyfunctional cooperation (see for instance ferrocenyl polyphosphine chemistry). Ansa ferrocene and ferrocene bearing conformational control inducing groups maximizing the proximity of key groups have been widely reported.The first part of this thesis focuses on the synthesis of new borylated cyclopentadienyl, and their use in formation of borylated metallocenes bearing conformational constraints. NMR analysis and DFT calculation exhibits the diastereoselectivity of assembly reaction.The second part deals with the arrangement of several Lewis acids and bases on a constraint ferrocene platform. Synthesis of trisubstituted cyclopentadienyl (P/B) has been initiated. Synthesis of ambiphilic ligands (P/B) by assembly reaction of cyclopentadienides and the influence of tert-butyl groups on their conformation have been explored. A new 31P31P spin coupling transmitted “through-space (nonbonded spin-spin coupling transmission) involving for the first time an empty orbital has been observed.The third part describes the synthesis of heteroannular (P/B) and (N/B) ferrocene directly from ferrocene functionalization. An efficient and diastereoselective synthesis has been developed and the influence of tert-butyl groups on the conformational control has been highlighted in both solid and solution state. Studies of the frustrated Lewis pair reactivity of these new ambiphilic ligands have been initiated by addition of CO2.
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Submitted on : Monday, November 12, 2018 - 1:01:44 AM
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  • HAL Id : tel-01918837, version 1



Emmanuel Lerayer. Synthèse et caractérisation de phosphine, borane, amine sur plateforme ferrocène polyfonctionnelle. Chimie de coordination. Université de Bourgogne, 2016. Français. ⟨NNT : 2016DIJOS051⟩. ⟨tel-01918837⟩



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