A donor-supported silavinylidene and silylium ylides: boroles as a flexible platform for versatile Si(<scp>ii</scp>) chemistry

Sarcevic, Julijan; Heitkemper, Tobias; Ruth, Paul Niklas; Naß, Leonard; Kubis, Maximilian; Sindlinger, Christian P.

doi:10.1039/d3sc00808h

“…[10][11][12] Als solche sind diese Verbindungen Beispiele für Hetero [5]pyramidane. [13][14][15] Derivate aller gemischten Carba-nido-Hexaborane von CB 5 H 9 bis zu [C 6 H 6 ] 2 + sind literaturbekannt [16][17][18][19][20] und die Reihe der Halbsandwichkomplexe der Elemente der Gruppen 13, 14 und 15 II sind Beispiele für die Implementierung anderer Hauptgruppenelemente in die Apexposition der nido-Struktur. [21][22][23][24][25][26][27][28][29][30][31][32][33][34] Borol-Germaniumkomplexe I [8][9] und ihre Zinn-und Siliciumanaloga [35][36] sind seltene Beispiele für Verbindungen mit anderen Hauptgruppenheteroatomen als Bor in Clusterstrukturen von [5]Pyramidanen.…”

Section: Introductionunclassified

“… [9] Diese Verbindungen können gleichermaßen als Halbsandwichkomplexe zwischen Ge(II) und Boroldianionen ( IA) oder, abgeleitet von nido ‐Hexaboran(10) ( IB ), als sechseckiger nido ‐Cluster beschrieben werden [10–12] . Als solche sind diese Verbindungen Beispiele für Hetero[5]pyramidane [13–15] …”

Section: Introductionunclassified

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Aluminagerma[5]pyramidane – Bildung und Gerüstumlagerung

Bührmann,

Albers,

Beuße

et al. 2024

Angewandte Chemie

0

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The salt metathesis reaction of dipotassium germacyclopentadienediide with aluminum(III) dichlorides provides either half‐sandwich alumole complexes of germanium(II) or aluminylene germole complexes. Their molecular structure and the delocalized bonding situation, revealed by density functional theory (DFT) calculations, are equally described as isomeric aluminagerma[5]pyramidanes with either the germanium or the aluminum atom in the apical position of the pentagonal pyramid. The product formation and the selectivity of the reaction depends on the third substituent of the aluminum dichloride. Aryl‐substituents favor the formation of alumole complexes and Cp*‐substituents that of the isomeric germole complexes. With amino‐substituents at the aluminum atom mixtures of both isomers are formed and the positional exchange of the two heteroatoms is shown by NMR spectroscopy. The alumole complexes of Ge(II) undergo facile reductive elimination of germanium and form the corresponding alumoles.

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“…[10][11][12] As such, these compounds are examples for hetero [5]pyramidanes. [13][14][15] Derivatives of all mixed carba-nido-hexaboranes from CB 5 H 9 up to [C 6 H 6 ] 2 + are known [16][17][18][19][20] and the series of halfsandwich complexes of group 13, 14 and 15 elements II are examples for inclusion of other main group elements at the apex position of the nido-structure. [21][22][23][24][25][26][27][28][29][30][31][32][33][34] Germanium borole complexes I [8][9] and their tin and silicon analogues [35][36] are rare examples for compounds with main group heteroatoms other than boron atoms included in the cluster architecture of [5]pyramidanes.…”

Section: Introductionmentioning

confidence: 99%

Aluminagerma[5]pyramidanes—Formation and Skeletal Rearrangement

Bührmann,

Albers,

Beuße

et al. 2024

Angew Chem Int Ed

2

0

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The salt metathesis reaction of dipotassium germacyclopentadienediide with aluminum(III) dichlorides provides either half‐sandwich alumole complexes of germanium(II) or aluminylene germole complexes. Their molecular structure and the delocalized bonding situation, revealed by density functional theory (DFT) calculations, are equally described as isomeric aluminagerma[5]pyramidanes with either the germanium or the aluminum atom in the apical position of the pentagonal pyramid. The product formation and the selectivity of the reaction depends on the third substituent of the aluminum dichloride. Aryl‐substituents favor the formation of alumole complexes and Cp*‐substituents that of the isomeric germole complexes. With amino‐substituents at the aluminum atom mixtures of both isomers are formed and the positional exchange of the two heteroatoms is shown by NMR spectroscopy. The alumole complexes of Ge(II) undergo facile reductive elimination of germanium and form the corresponding alumoles.

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“…[2] Over the past decade, heavier analogues of vinylidenes (R 2 E=E:, E=Si, Ge, Sn) have been isolated and characterized structurally taking advantage of the base-stabilization concept. [4][5][6][7][8][9][10] Recently, Aldridge et al reported a base-free digermavinylidene utilizing an electron-donating boryl ligand, which was generated by the rearrangement of the transient digermyne isomer via 1,2-boryl migration (Scheme 1a). [11] Double 1,2-migration involving the migration of two groups from the same atom to the adjacent atom is far less prevalent.…”

mentioning

confidence: 99%

Double 1,2‐Carbon Migration at Mixed Heavier Sn=Ge Vinylidenes

Qiao,

Li,

Chen

et al. 2024

Angewandte Chemie

0

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1,2‐migration is one recurring isomerization reaction in organic chemistry. In contrast, double 1,2‐migration remains rare and limited to transition‐metal complexes. Herein, we describe the synthesis, characterization and reactivity of mixed heavier Sn=Ge vinylidenes. Double 1,2‐carbon migration enables the isomerization of the stannagermenylidene (3) to the germastannenylidene (4). X‐ray diffraction analysis and DFT calculations revealed that 3 and 4 feature a Sn=Ge double bond. The reaction of 3 with IMe2 (1,3,4,5‐tetramethylimidazoline‐2‐ylidene) results in the electron redistribution in the Sn=Ge core to give the germylone‐stannylene adduct (5). Moreover, treatment of 3 with 0.25 equiv. of (AlCp*)4 produces the heteronuclear aluminyl stannagermyne (6).

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A donor-supported silavinylidene and silylium ylides: boroles as a flexible platform for versatile Si(ii) chemistry

Abstract: Electron-deficient, anti-aromatic 2,5-disilyl boroles are shown to be a flexibly adaptive molecular platform with regards to SiMe3 mobility in their reaction with a nucleophilic donor-stabilised precursor of dichloro silylene SiCl2(IDipp)....

Cited by 6 publications

References 100 publications

Aluminagerma[5]pyramidane – Bildung und Gerüstumlagerung

Aluminagerma[5]pyramidane – Bildung und Gerüstumlagerung

Aluminagerma[5]pyramidanes—Formation and Skeletal Rearrangement

Double 1,2‐Carbon Migration at Mixed Heavier Sn=Ge Vinylidenes

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