Manipulating the Substituent Sphere of a Bicyclic Silicon(I) Ring Compound Results in Anionic Cubane-Type Clusters and a Tetrahedral Silanide.

Autor: Quest M; Universität Münster, Institut für Anorganische und Analytische Chemie, Corrensstraße 28-30, 48149, Münster, Germany., Hepp A; Universität Münster, Institut für Anorganische und Analytische Chemie, Corrensstraße 28-30, 48149, Münster, Germany., Hebenbrock M; Universität Münster, Institut für Anorganische und Analytische Chemie, Corrensstraße 28-30, 48149, Münster, Germany., Daniliuc CG; Universität Münster, Organisch-Chemisches Institut, Corrensstraße 40, 48149, Münster, Germany., Bresien J; Universität Rostock, Institut für Chemie, Albert-Einstein-Straße 3a, 18059, Rostock, Germany., Lips F; Universität Münster, Institut für Anorganische und Analytische Chemie, Corrensstraße 28-30, 48149, Münster, Germany.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Nov 21; Vol. 30 (65), pp. e202400368. Date of Electronic Publication: 2024 Nov 03.
DOI: 10.1002/chem.202400368
Abstrakt: The reaction of the bicyclic silicon(I) ring compound Si 4 {N(SiMe 3 )Mes} 4 1 with strong zwitterionic character and moderate sterical demand of the amido substituents with two equivalents of KC 8 was investigated. This resulted in the unexpected abstraction of two amido substituents from 1 and additionally in dimerization to a dianionic Si 8 cluster compound 2 with four unsubstituted silicon atoms and two [K([18]crown-6)] + counter cations. Performing this reaction in the absence of [18]crown-6 results in release of only one amido substituent from 1 and dimerization to a dianionic Si 8 cluster 3 with only two unsubstituted silicon atoms. This reaction with KC 8 was repeated and trapping agents such as SiMe 3 Cl and tBuCl were added in-situ whereupon the second isolated homocyclic silylene 4 and a monoanionic hydride and tBu substituted Si 8 cluster 5 with one unsubstituted silicon atom were isolated. Furthermore, 1 was reacted with KOtBu which resulted in the selective abstraction of one SiMe 3 group and formation of the tetrahedral silanide 6 with one imido substituent bridging an edge of the tetrahedron.
(© 2024 The Author(s). Chemistry - A European Journal published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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