Spirocyclic germanes <i>via</i> transannular insertion reactions of vinyl germylenes into Si–Si bonds

Walewska, Małgorzata; Baumgartner, Judith; Marschner, Christoph; Albers, Lena; Müller, Thomas

doi:10.1039/c8dt00315g

Cited by 7 publications

(9 citation statements)

References 48 publications

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“…To the best of our knowledge and based on a search in the Cambridge structural database a germastannacyclobutene ring is so far unknown. However, examples for the silagermete ring molecule were already published in the literature [2k, o, 27] . The Sn−Ge bond length of 2.669(1) Å is comparable to the Sn‐Ge bond length found in 1 [2.6686(3) Å] and slightly shorter than distances reported for a germylenestannylene [2.721(1) Å] or germylstannylenes [2.722(1), 2.746(1) Å] [28] .…”

Section: Resultsmentioning

confidence: 66%

Tetryl‐Tetrylene Addition to Phenylacetylene

Maudrich

Diab

Weiß

et al. 2021

Chemistry A European J

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Phenylacetylene adds [Ar*GeH2‐SnAr’], [Ar*GeH2‐PbAr’] and [Ar'SnH2‐PbAr*] at rt in a regioselective and stereoselective reaction. The highest reactivity was found for the stannylene, which reacts immediately upon addition of one equivalent of alkyne. However, the plumbylenes exhibit addition to the alkyne only in reaction with an excess of phenylacetylene. The product of the germylplumbylene addition reacts with a second equivalent of alkyne and the product of a CH‐activation, a dimeric lead acetylide, were isolated. In the case of the stannylplumbylene the trans‐addition product was characterized as the kinetically controlled product which isomerizes at rt to yield the cis‐addition product, which is stabilized by an intramolecular Sn–H–Pb interaction. NMR chemical shifts of the olefins were investigated using two‐ and four‐component relativistic DFT calculations, as spin–orbit effects can be large. Hydride abstraction was carried out by treating [Ar'SnPhC=CHGeH2Ar*] with the trityl salt [Ph3C][Al(OC{CF3})4] to yield a four membered ring cation.

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Section: Resultsmentioning

confidence: 66%

Tetryl‐Tetrylene Addition to Phenylacetylene

Maudrich

Diab

Weiß

et al. 2021

Chemistry A European J

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“…The same reaction could be also carried out with trimethylsilylactylene and 1-hexyne (Scheme 1) [13]. When phosphane adducts of cyclic disilylated germylenes were subjected to reactions with alkynes spirocyclic, vinylgermanes were obtained [14]. Similar alkyne insertion reactivity was later observed for a diborylstannylene [15].…”

Section: Introductionmentioning

confidence: 78%

1,2- and 1,1-Migratory Insertion Reactions of Silylated Germylene Adducts

2020

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The reactions of the PMe3 adduct of the silylated germylene [(Me3Si)3Si]2Ge: with GeCl2·dioxane were found to yield 1,1-migratory insertion products of GeCl2 into one or two Ge–Si bonds. In a related reaction, a germylene was inserted with tris(trimethylsilyl)silyl and vinyl substituents into a Ge–Cl bond of GeCl2. This was followed by intramolecular trimethylsilyl chloride elimination to another cyclic germylene PMe3 adduct. The reaction of the GeCl2 mono-insertion product (Me3Si)3SiGe:GeCl2Si(SiMe3)3 with Me3SiC≡CH gave a mixture of alkyne mono- and diinsertion products. While the reaction of a divinylgermylene with GeCl2·dioxane only results in the exchange of the dioxane of GeCl2 against the divinylgermylene as base, the reaction of [(Me3Si)3Si]2Ge: with one GeCl2·dioxane and three phenylacetylenes gives a trivinylated germane with a chlorogermylene attached to one of the vinyl units.

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“…[28] Scheme4.Synthesis of germylene (thf)Ge[S-GeCl 2 -Tsi] 2 (4)a long two different reaction pathways. 3), Ge1ÀO1 208.0(2), Ge2ÀCl1 217.64(9); S2-Ge1-S1 86.02(3),G e1-S1-Ge2 98.03(3),S 1-Ge2-C1 117.51(9),C l1-Ge2-Cl299.78 (4).…”

Section: Resultsmentioning

confidence: 99%

“…For the stabilization of silylated germylenes, phosphines such as in (Me 3 P)Ge[Si(SiMe 3 ) 3 ] 2 are a good choice, in which the strong interaction between the germylene and the phosphine leads to a stabilization of the Ge II species. However, the phosphines can still dissociate for further reactions . Bulky aryl substituents, such as terphenyl substituents, can sterically protect the germylenes without inducing destabilizing distortions .…”

Section: Introductionmentioning

confidence: 99%

“…However,t he phosphines can still dissociate for furtherr eactions. [4] Bulky aryl substituents, such as terphenyl substituents, can sterically protect the germyleneswithout inducing destabilizing distortions. [5] Furthermore,N -heterocyclic carbenea nalogues of germanium are wellk nown,a sh ere the low-valent germaniums peciesi ss tabilized by p donation of electrond ensity from the attached nitrogen atom lone pairs into the empty po rbital at the germaniuma tom.…”

Section: Introductionmentioning

confidence: 99%

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Reactions of GeCl₂ with the Thiolate LiSC(SiMe₃)₃: From thf Activation to Insertion of GeCl₂ Molecules into C−S Bonds

Kunz

Schrenk

Schnepf

2019

Chemistry A European J

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The reaction system GeCl2⋅dioxane/LiSTsi (Tsi=C(SiMe3)3) opens a fruitful area in germanium chemistry, depending on the stoichiometry and solvent used during the reaction. For example, the reaction of GeCl2⋅dioxane in toluene with two equivalents of the thiolate gives the expected germylene Ge(STsi)2 in excellent yield. This germylene readily reacts with hydrogen and acetylene, however, in a non‐selective way. By using an excess amount of the thiolate and toluene as the solvent, the germanide [Ge(STsi)3][Li(thf)] is obtained. Performing the same reaction in thf leads to a C−H activation of thf to give (H7C4O)Ge[STsi](μ2‐S)2Ge[STsi]2, in which the thf molecule is still intact. Using a sub‐stoichiometric amount of the thiolate leads to the heteroleptic compound [ClGe(STsi)]2 and to the insertion product (thf)Ge[S‐GeCl2‐Tsi]2, in which additional GeCl2 molecules insert into the C−S bonds of Ge(STsi)2. The synthesis and the experimentally determined structures of all compounds are presented together with first reactivity studies of Ge(STsi)2.

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Spirocyclic germanes via transannular insertion reactions of vinyl germylenes into Si–Si bonds

Abstract: The reaction of cyclic disilylated germylene phosphane adducts with alkynes gives spirocyclic germanes via the intermediate formation of cyclic divinylgermylenes.

Cited by 7 publications

References 48 publications

Tetryl‐Tetrylene Addition to Phenylacetylene

Tetryl‐Tetrylene Addition to Phenylacetylene

1,2- and 1,1-Migratory Insertion Reactions of Silylated Germylene Adducts

Reactions of GeCl₂ with the Thiolate LiSC(SiMe₃)₃: From thf Activation to Insertion of GeCl₂ Molecules into C−S Bonds

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Spirocyclic germanes via transannular insertion reactions of vinyl germylenes into Si–Si bonds

Abstract: The reaction of cyclic disilylated germylene phosphane adducts with alkynes gives spirocyclic germanes via the intermediate formation of cyclic divinylgermylenes.

Cited by 7 publications

References 48 publications

Tetryl‐Tetrylene Addition to Phenylacetylene

Tetryl‐Tetrylene Addition to Phenylacetylene

1,2- and 1,1-Migratory Insertion Reactions of Silylated Germylene Adducts

Reactions of GeCl2 with the Thiolate LiSC(SiMe3)3: From thf Activation to Insertion of GeCl2 Molecules into C−S Bonds

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Reactions of GeCl₂ with the Thiolate LiSC(SiMe₃)₃: From thf Activation to Insertion of GeCl₂ Molecules into C−S Bonds