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Complexes de métaux électropositifs à travers le prisme du groupe cyclopropyle

Abstract : The manuscript presents the chemistry of electropositive metal complexes bearing the cyclopropyl group. This first part of the manuscript describes the synthesis and characterisation of cyclopropopyllithium derivatives of the formula [1-R-c-C3H4Li] (R = SiMe3, Ph, SPh). Original aggregates displaying low valent Li+ centres stabilised by the rare CC agostic interaction are presented. This interaction influences the aggregation of the compounds in the solid state and sometimes in solution. A qualitative evaluation of its strength is provided by competitive coordination on Li+ vs donor atoms such as O, N and S. The second part of the manuscript presents the synthesis of the new cyclopropylcalcium complex. This compound is characterised by a full NMR study. It is the first non-stabilised alkylcalcium compound. The third part of the manuscript contains a reactivity study of dicyclopropylzirconocene [Cp2Zr(c-C3H5)2] towards pyridine and fluorinated pyridines. Dearomatisation and C-H bond activation of pyridine, together with C-F bond activation of pentafluoropyridine result from the initial formation of a Eta2-cyclopropene intermediate. A preliminary study of the catalytic C-F bond cleavage of pentafluoropyridine by [Cp2Zr(c-C3H5)2] in the presence of tricyclopropylaluminium is also presented.
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Submitted on : Friday, January 19, 2018 - 3:30:30 PM
Last modification on : Friday, February 14, 2020 - 4:18:58 AM
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  • HAL Id : tel-01688622, version 1



Quentin Dufrois. Complexes de métaux électropositifs à travers le prisme du groupe cyclopropyle. Chimie de coordination. Université Paul Sabatier - Toulouse III, 2016. Français. ⟨NNT : 2016TOU30303⟩. ⟨tel-01688622⟩



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