Sabrina Jeltsch, Jannik Schulz, Claudio Schrenk, Andreas Schnepf
{"title":"Insertion Behavior of Dialkylgermylene Ge(FluTMS)2 in Different E–X σ Bonds (E = Au, Si, Ge, Sn) and Its Relevance for Germanium Cluster Formation","authors":"Sabrina Jeltsch, Jannik Schulz, Claudio Schrenk, Andreas Schnepf","doi":"10.1021/acs.inorgchem.4c04099","DOIUrl":null,"url":null,"abstract":"We present the insertion behavior of the alkyl-substituted germylene Ge(Flu<sup>TMS</sup>)<sub>2</sub> in different E–X σ bonds (E = Au, Si, Ge, Sn), first with the isolation of the germylgold complex (Flu<sup>TMS</sup>)<sub>2</sub>Ge(Cl)AuPPh<sub>3</sub>. Afterward, the oxidative addition of GeCl<sub>4</sub> to Ge(Flu<sup>TMS</sup>)<sub>2</sub> gives the digermane (Flu<sup>TMS</sup>)<sub>2</sub>Ge(Cl)GeCl<sub>3</sub>, followed by a reductive elimination of GeCl<sub>2</sub> and the formation of the oxidation product (Flu<sup>TMS</sup>)<sub>2</sub>GeCl<sub>2</sub>. A comparable behavior is observed, with the homologues ECl<sub>4</sub> (E = Si, Sn) stopping at different steps of the reaction. The formation of the germylgermylene (Flu<sup>TMS</sup>)<sub>2</sub>Ge(Cl)GeCl starting from Ge(Flu<sup>TMS</sup>)<sub>2</sub> and GeCl<sub>2</sub>·dioxane is also spectroscopically observable, followed by ligand rearrangements to the tetramer [Flu<sup>TMS</sup>GeCl]<sub>4</sub>. Adding a phosphine as the Lewis base has a direct influence on the stability and structure of (Flu<sup>TMS</sup>)<sub>2</sub>Ge(Cl)GeCl, leading to the formation of Flu<sup>TMS</sup>GeCl·PEt<sub>3</sub> as a stable product. Subsequent investigations of Ge(Flu<sup>TMS</sup>)<sub>2</sub> with a metastable Ge(I)Br solution show that at a ratio of 6:1 GeBr/Ge(Flu<sup>TMS</sup>)<sub>2</sub> 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.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"51 1 1","pages":""},"PeriodicalIF":4.3000,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.inorgchem.4c04099","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
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.
期刊介绍:
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.