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1,4-Disilabutane H 3 SiCH 2 CH 2 SiH 3  (1) and n-tetrasilane H 3 SiSiH,SiH 2 SiH 3  were employed as model systems for the preparation of silicon-rich aminosilanes potentially useful for the deposition of silicon nitride Si 3 N 4 . 1 reacts with the appropriate equivalents of diethylamine in an alkane solvent and in the presence of the two-phase catalyst NaNH 2 /18-crown-6 to give the products (Et,N) 2 SiHCH 2 CH 2 SiH 3 , (Et 2 N) 2 SiHCH 2 CH 2 SiH 2 (NEt 2 ), and (Et 2 N) 2 SiHCH 2 CH 2 SiH(NEt 2 ) 2 . By contrast, n-Si 4 H 10  undergoes a cleavage reaction under similar conditions to yield H 3 SiNEt 2  and H 2 Si(NEt 2 ) 2  together with a mixture of polysilanes Si n H 2n+2 , the composition of which is depending on the reaction conditions and the nature of the catalyst (NaH and NaNH 2 ). Diethylaminopolysilanes are also formed, but only in trace quantities. Treatment of n-Si 4 H 10  with pyrrole (C 4 H 5 N) leads to the formation of trisilane accompanied by the pyrrolylsilanes H 2 Si(C 4 H 4 N) 2 , HSi(C 4 H 4 N) 3 , and Si(C 4 H 4 N) 4 . The differences in reactivity suggest excellent leaving group properties of silyl anions in the reaction with amines.

zeitschrift für naturforschung b

Die unterschiedliche Reaktivität von 1,4-Disilabutan und n-Tetrasilan gegenüber sekundären Aminen / Differences in Reactivity of 1,4-Disilabutane and n-Tetrasilane towards Secondary Amines