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Updated: Jun 5, 2025

Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups
Published on: February 11, 2012
Insertion Behavior of Dialkylgermylene Ge(FluTMS)2 in Different E-X σ Bonds (E = Au, Si, Ge, Sn) and Its Relevance
Sabrina Jeltsch1, Jannik Schulz1, Claudio Schrenk1
1Chemistry Department, University of Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany.
Abstract:
We present the insertion behavior of the alkyl-substituted germylene Ge(FluTMS)2 in different E-X σ bonds (E = Au, Si, Ge, Sn), first with the isolation of the germylgold complex (FluTMS)2Ge(Cl)AuPPh3. Afterward, the oxidative addition of GeCl4 to Ge(FluTMS)2 gives the digermane (FluTMS)2Ge(Cl)GeCl3, followed by a reductive elimination of GeCl2 and the formation of the oxidation product (FluTMS)2GeCl2. A comparable behavior is observed, with the homologues ECl4 (E = Si, Sn) stopping at different steps of the reaction. The formation of the germylgermylene (FluTMS)2Ge(Cl)GeCl starting from Ge(FluTMS)2 and GeCl2·dioxane is also spectroscopically observable, followed by ligand rearrangements to the tetramer [FluTMSGeCl]4. Adding a phosphine as the Lewis base has a direct influence on the stability and structure of (FluTMS)2Ge(Cl)GeCl, leading to the formation of FluTMSGeCl·PEt3 as a stable product. Subsequent investigations of Ge(FluTMS)2 with a metastable Ge(I)Br solution show that at a ratio of 6:1 GeBr/Ge(FluTMS)2 the alkyl-substituted germylene no longer acts as a redox-active agent but as a cluster building block. This link and the involvement of a germylene in insertion reactions give an indication of how the construction or expansion of Ge cluster species can operate.
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