Formation and Properties of a Bicyclic Silylated Digermene

Hlina, Johann; Baumgartner, Judith; Marschner, Christoph; Albers, Lena; Müller, Thomas; Jouikov, Viatcheslav

doi:10.1002/chem.201402785

Cited by 31 publications

(40 citation statements)

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“…Based on initial studies with cyclic disilylated stannylenes and plumbylenes, our work included PEt 3 and PMe 3 adducts of some cyclic disilylated germylenes and the recent synthesis of PMe 3 and NHC adducts of bis[tris(trimethylsilyl)silyl]germylene …”

Section: Resultsmentioning

confidence: 99%

“…The use of NHCs to form stable adducts of silylated silylenes, germylenes, and stannylenes has been demonstrated before. In the current study NHC adduct formation was also used to obtain stable derivatives from the rather labile germylene–phosphine adducts.…”

Section: Resultsmentioning

confidence: 99%

“…[14] However,r ecently NHC adducts of at ris(trimethylsilyl)silylchlorogermylene and bis[tris(trimethylsilyl)stannyl]germylene were reported. [15] Based on initial studies with cyclic disilylated stannylenes [16] and plumbylenes, [17] our work included PEt 3 and PMe 3 adducts of some cyclic disilylatedg ermylenes [18][19][20][21] and the recent synthesis of PMe 3 and NHC adducts of bis[tris(trimethylsilyl)silyl]germylene. [6] The synthesis of 2a,w hich is the PMe 3 adduct of bis[tris(trimethylsilyl)silyl]germylene 2,was accomplished in astraightforward way by reaction of tris(trimethylsilyl)silylpotassium (1) with GeCl 2 ·dioxane in the presence of PMe 3 (Scheme1).…”

Section: Introductionmentioning

confidence: 99%

“…The use of NHCs to form stable adducts of silylated silylenes, [22,23] germylenes, [6,[18][19][20] and stannylenes [15] has been demonstrated before.I nt he current study NHC adduct formation was also used to obtain stable derivatives from the rather labile germylene-phosphine adducts. The strongeri nteraction between the NHC and germylene units prevents dissociation of the base and allows easier handling and characterization.…”

Section: Introductionmentioning

confidence: 99%

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Alkyne Addition and Insertion Reactions of [(Me₃Si)₃Si]₂Ge⋅PMe₃

Walewska

Baumgartner

Marschner

et al. 2016

Chemistry A European J

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Silylated germylene–PMe3 adducts exchange their phosphane moiety smoothly for an N‐heterocyclic carbene or isocyanide species to form their respective base adducts. Reaction of the silylated germylene–PMe3 adducts with monosubstituted alkynes produce germylene adducts with the alkyne inserted into a Ge−Si bond. A computational study of this process provides evidence for the initial formation of a germirene, which rearranges to a vinylgermylene species. The thermodynamic driving force for this reaction is provided by subsequent adduct formation with PMe3. Reaction of the PMe3 adduct of bis[(trimethylsilyl)silyl]germylene with disubstituted alkynes leads to the formation of stable germirenes, which can be isomerized further to silagermetes.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Alkyne Addition and Insertion Reactions of [(Me₃Si)₃Si]₂Ge⋅PMe₃

Walewska

Baumgartner

Marschner

et al. 2016

Chemistry A European J

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“…One particularly interesting class of compounds in this chemistry is that of heavier divalent group 14 compounds (tetrylenes) , . Our own recent studies focus on silylated tetrylenes, first examples of which were reported by Klinkhammer and Schwarz , who prepared bis[tris(trimethylsilyl)silyl]stannylene and ‐plumbylene …”

Section: Introductionmentioning

confidence: 99%

NHC Adducts of Disilylated Germylenes and Stannylenes and Their Coordination Chemistry with Group 11 Metals

Walewska

Hlina

Gaderbauer

et al. 2016

Zeitschrift anorg allge chemie

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Syntheses of NHC adducts of bis[tris(trimethylsilyl)silyl]germylene and -stannylene and some structurally related cyclic disilylated stannylenes are reported. Reactions of a cyclic stannylene NHC adduct with gold and silver cyanide led to cationic metal complexes with two cyanostannyl ligands. The Ag complex decomposed 1304 further to a cyanostannide. Reactions of bis[tris(trimethylsilyl)silyl]germylene and -stannylene NHC adducts with gold and silver cyanide displayed more unusual coordination chemistry with one silyl group of the ylene unit being transferred to the group 11 metal.One particularly interesting class of compounds in this chemistry is that of heavier divalent group 14 compounds (tetrylenes). [12,13] Our own recent studies focus on silylated tetrylenes, [14][15][16][17][18][19][20][21][22][23][24][25] first examples of which were reported by Klinkhammer and Schwarz, who prepared bis[tris(trimethylsilyl)silyl]stannylene and -plumbylene. [26] While Klinkhammer found that bis[tris(trimethylsilyl)silyl]stannylene is monomeric in solution our own attempts to prepare a cyclic variation of this compound showed that dimerization occurred. [14] In order to prevent the dimerization process we carried out the preparation in the presence of triethylphosphane, which led to the formation of a stannylene base adduct. [14] Klinkhammer reported that bis[tris(trimethylsilyl)silyl]stannylene also undergoes adduct formation with phosphanes [27] and later Castel, Escudié, and co-workers demonstrated that even NHC adducts of the compound can be obtained. [28] Results and DiscussionAs mentioned, Klinkhammer already reported phosphane adduct formation of bis[tris(trimethylsilyl)silyl]stannylene. [27,29] Recently we have described synthesis and characterization of a triethylphosphane adduct [17] and also the respective trimethylphosphane adduct 2 is easily accessible from the reaction of 2 equiv. of tris(trimethylsilyl)silylpotassium (1) with SnCl 2 in the presence of PMe 3 (Scheme 1). Scheme 1. Synthesis of bis[tris(trimethylsilyl)silyl]stannylene and germylene base adducts. Journal of Inorganic and General ChemistryZeitschrift für anorganische und allgemeine Chemie www.zaac.wiley-vch.de ARTICLE Analogous reactions of 1 with SnCl 2 or GeBr 2 in the presence of 1,3,4,5-tetramethylimidazol-2-ylidene ( Me IMe) gave the respective NHC adducts 3 [25] and 4 (Scheme 1). Syntheses of the analogous 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene ( Me IPr) stannylene [28] and germylene [21] adducts were reported before. Single crystal diffraction analysis of 2 ( Figure 1) and 4 ( Figure 2) provided structural proof.

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