Lithio‐aminofluorsilane werden in der Reaktion von Aminofluorsilanen mit Butyllithium erhalten. Die thermische LiF‐Abspaltung aus Lithio‐aminofluorsilanen ist ein einfacher Syntheseweg für viergliedrige Silicium‐Stickstoff‐Ringe. Röntgenstrukturuntersuchungen wurden von 1,3‐Bis(3,5‐dimethylphenyl)‐2,2,4,4‐tetramethyl‐1,3‐diaza‐2,4‐disilacyclobutan und von 2,4‐Di‐tert.‐butyl‐2,4‐difluor‐1,3‐bis(2,4,6‐trimethylphenyl)‐1,3‐diaza‐2,4‐disiacyclobutan durchgeführt.
C21H24F3N3Si3, Mr=459.7, trigonal, R3, a = 8.589 (2) A, ct = 102.53 (2) °, U = 580.2 A 3, z = 1, D x = 1.316 Mg m-3; final R = 0.055 for 459 reflexions. The molecule has a crystallographic threefold axis. The central Si3N 3 ring is almost planar with Si-N = 1.700 (6)A, and internal angles of 110.1 (5) and 129.8 (5) ° at Si and N. Abstract. C26H2002, Mr=364, monoclinic, P2Jn,
Reactions of dichlorodiorganosilanes with ammonia proceed with complete cleavage of hydrogen chloride to afford six-and eight-membered cyclosilazanes and higher condensation products"]. Sterically demanding substituents lead to short-chain acyclic silazanes[21. In this connection neither the formation of a four-membered ring [R2Si-NHI2 nor of an intermediate product R2SiCI-NH2 has been observed.Cyclosilaphosphanes were obtained by reaction of dichlorodiorganosilanes with lithium phosphide or metalated organoph~sphanes~'~. The annelation can be attributed to the marked tendency of the initially formed unstable diphosphinosilanes to rearrange, although bis(tert-butylphosphino)dimethylsilane, Me2Si(PHtBu),, has been isolated and after lithiation used in the synthesis of cyclosilaphosphanes"].By allowing difluorodiorganosilanes to react with lithium amide or lithium phosphide, we obtained the surprisingly stable N-(fluorosily1)amines 1 and 2, and the N-(fluorosi1yl)phosphane 3 (b.p.=55 "C/18 torr, 38 "C/19 torr, and 70 "C/4 torr).In an analogous fashion to the isoelectronic compound (~Bu),S~F(OH)['~, 1 and 3 show no tendency to condense.
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