Beiträge zur Chemie der Silicium‐Stickstoff‐Verbindungen. C. Die partielle Ammonolyse des Siliciumtetrachlorids Hexachlordisilazan. Hexachlorcyclotrisilazan

Abstract

Die partielle Ammonolyse you Siliciumtetrachlorid in Diäthyläther <−60° führt zu Hexachlordisilazan (I; 40% Ausbeute), Hexachlorcyclotrisilazan (II; 3–5%) und Polychlorsilazanen, vornehmlich [Ci2SiNH]x (III). Einen Überblick über die einzelnen Reaktionsschritte gibt Schema 2. Durch Spaltung von III mit HCl oder HBr in Benzol oder Äther bzw. mit SiCl4 unter erhöhten Temperaturen und Drücken entsteht weiteres I in bescheidenen und Oktachlortrisildiazan (IV) in sehr geringen Ausbeuten. I bildet mit Butyllithium Lithium‐bis‐(trichlorsilyl)amid (IX). Dieses reagiert mit Schwerem Wasser zu Deuterohexachlordisilazan (V) und zerfällt beim Erwärmen in LiCl und Dekachlor‐bis(silyl)‐cyclodisilazan (XIX). Physikalische Daten und Analysen dieser Verbindungen sind in Tab. 2 und 3 zusammengefaßt. Weitere Reaktionen von I. II und IX können aus Kap. 4a. b sowie Schema 3, 4 und 6 ersehen werden.

Amorphous Multinary Ceramics in the Si-B-N-C System

“…Subsequent reaction of the lithium amide with a suitable element halide provides the desired precursor, while the lithium halide is eliminated (Eq. 5) [25,27]: For the formation of carbon-boron bonds basically two reaction types are of importance: hydroboration and transmetallation (salt elimination). An elegant route to alkyldihaloboranes has been introduced by Soundararajan and Matteson [28,29], who employed a mixture of trichloroborane and trialkylsilane to generate HBC1 2 in situ.…”

Trichlorosilyl Anions of p‐Block Elements – New Applications for Simple Molecules

“…The compound can be synthesized in a high temperature synthesis between SiCl 4 and NH 3 [66–68] . Other variants use low‐temperature reactions in diethyl ether [69,70] . Reactions of hexachlorodisilazane with lithium, zinc, cadmium organyls and other reagents show the ability to form metal amides like other amines [70,71] .…”

“…Wider use of hexachlorodisilazane was probably prevented by the difficult synthesis. The ammonolysis reaction between SiCl 4 and NH 3 leads always to a complex product mixture, wherefrom it seems to be difficult to isolate hexachlorodisilazane [70] …”

“…[66][67][68] Other variants use low-temperature reactions in diethyl ether. [69,70] Reactions of hexachlorodisilazane with lithium, zinc, cadmium organyls and other reagents show the ability to form metal amides like other amines. [70,71] Reactions with pyridine, NMe 3 or NEt 3 yield ammonium salts.…”

The Silicon-Nitrogen Bond

“…IMPORTANT CLASSES OF SILICON-NITROGEN COMPOUNDS (16) It is possible to surround a silicon atom with up to four N atoms (mainly alkyla~no -NHR or dialkylamino groups -NR 2 groups, and seldomly with arylamino groups). With a nitrogen atom one has up to three Si atoms (trialkylsilyl groups -SiR3 in most cases).…”