Treatment of hexakis(2,4,6-triisopropylphenyl)tetrasilabuta-1,3-diene (1), R 2 Si=SiR±SiR=SiR 2 , with ammonia and chlorine furnishes the correspondingly substituted 1,4diaminotetrasilane (3) and 1,2,3,4-tetrachlorotetrasilane (6). While product 6 crystallizes as a racemate, 3 forms a con-glomerate of enantiomerically pure crystals. The change of colors during the formation of 6 indicates a stepwise reaction sequence.
Ammoniak-und Chloradditionen an ein Tetrasilabuta-1,3-dien: Konglomerat versus Racemat-Kristallisation [1]Inhaltsu È bersicht. Die Reaktion von Hexakis(2,4,6-triisopropylphenyl)tetrasilabuta-1,3-dien R 2 Si=SiR±SiR=SiR 2 mit Ammoniak oder Chlor ergibt das entsprechend substituierte 1,4-Diaminotetrasilan (3) und das 1,2,3,4-Tetrachlortetrasilan (6). Wa È hrend 6 als Racemat kristallisiert, bildet 3 ein Konglomerat enantiomerenreiner Kristalle. Der Farbwechsel wa È hrend der Bildung von 6 deutet auf eine schrittweise verlaufende Reaktionssequenz hin.
The formal [4+1] cycloaddition of the chalcogens S, Se, and Te to the tetrasilabuta‐1,3‐diene 1 furnishes the molecules 2–4, the first five‐membered rings with endocyclic Si−Si double bonds. The new compounds are thermally stable and chemically inert. However, 4 is light‐sensitive and decomposes in daylight with deposition of tellurium. R=2,4,6‐iPr3C6H2.
Durch formale [4+1]‐Addition der Chalkogene S, Se und Te an das Tetrasilabuta‐1,3‐dien 1 entstehen die Verbindungen 2–4 als erste Fünfringe mit endocyclischen Si‐Si‐Doppelbindungen. Alle Verbindungen sind thermisch stabil und chemisch inert; lediglich 4 zersetzt sich an Licht unter Tellurabscheidung. R=2,4,6‐iPr3C6H2.
1,3-Digermabicyclo[1.1.0]butane 2 was synthesized as yellow crystals. The molecular structure, 13C NMR and UV–vis spectra, and theoretical calculations have revealed that 2 is a typical long bond isomer, similarly to the silicon congener 1. Structural comparison between 1 and 2 is achieved.
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