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Abstract : This work consists in a study of new tetra and divalent germanium species in an unusual coordination state.
The first chapter is a bibliographic review situating this work in the general context of the >E14 divalent species. It particularly concerns i) halogenated heteroleptic divalent species L2(Cl)Ge stabilized by the β-diketiminato ligand L2, ii) germanium derivatives bearing O-chelating “pincer” type ligands.
The second chapter concerns the germanium(II)-tungsten complexes [L2(X)Ge]nW(CO)6-n (L2 = NPhC(Me)CHC(Me)NPh ; n = 1, 2 ; X = Cl). Metathesis reactions of these complexes with low coordinating anions (TfO-, BPh4-, PF6-) are envisaged to obtain the corresponding cationic germanium complexes [L2Ge]n+W(CO)6-n. Structures of two germanium(II)-tungsten complexes are reported and analyzed. An equilibrium between a covalent and an ionic forms of the triflate derivatives is observed in pyridine.
The third chapter presents the synthesis and spectroscopic studies (IR ; Mass ; 1H, 13C, 17O NMR) of the 2-methoxybenzyl germanium(IV) compounds ArCH2GeHnΣn-3 (Ar = 2-(MeO)C6H4; n = 0 et 3, Σ = X, Me, Ph, OMe ; n = 1, Σ = X, Me, Mes, OMe, OTf ; n = 2, Σ = Cl). The spectroscopic studies, X-ray structure of ArCH2GeH2OTf and a DFT theoretical study show that the 2-méthoxybenzyl ligand adopts in these compounds a geometry allowing interaction between the methoxy moiety and the germanium center. This chapter also describes the synthesis of new divalent heteroleptic species 2-(MeO)C6H4CH2Ge(Cl) et 5-(Cl)-2-(MeO)C6H3CH2Ge(Cl) and some aspects of their reactivity. The structural analyses of a new type of cluster – structure with an hexacoordinated germanium(IV) and nine tricoordinated germanium(II) – obtained by slow hydrolysis reaction of a mixture of ArCH2GeHCl2 and Et3GeOMe is also presented.
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Submitted on : Monday, December 10, 2007 - 11:08:25 AM
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  • HAL Id : tel-00195193, version 1



Sonia Garcia Alonso. COORDINENCES NON USUELLES DU GERMANIUM. Autre. Université Paul Sabatier - Toulouse III, 2006. Français. ⟨tel-00195193⟩



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