180508-31-0Relevant academic research and scientific papers
Mono-, Bis-, Tris-, Tetrakis(silyl)hydrazine, Bis- und Tris(hydrazino)silane: Synthese und Kristallstrukturen
Bode, Katrin,Klingebiel, Uwe,Witte-Abel, Henning,Gluth, Matthias,Noltemeyer, Mathias,Herbst-Irmer, Regine,Schaefer, Martina,Shomaly, Walid
, p. 121 - 140 (2007/10/03)
Bulky fluorosilanes react with monolithiated hydrazine to give the stable mono(silyl)hydrazines H2N-NHR 1-3 .In a condensation reaction the symmetric bis(silyl)hydrazines 4 and 5 are obtained by 2 and 3 losing hydrazine.The reaction of lithiated 1, 2 and 3 with fluorosilanes leads to the formation of the asymmetric bis(silyl)hydrazines RHN-NHR', 6-10 .The lithium derivatives of N,N'-bis(tert-butyldimethylsilyl)hydrazine (11) and N-tert-butyl-N'-trimethylsilylhydrazine (12) have been isolated and the crystal structures have been determined.In the reaction of 12 with difluorodimethylsilane and tert-butylfluorodimethylsilane and substitution products (CMe3)HN-N(SiMe3)R 13 and 14 are formed .The tris(silyl)hydrazines 15 and 16 are formed in the reaction of 11 with SiF4 (15) and PhSiF3 (16).Lithiated 6 reacts with PhSiF3 to give the structural isomers RHN-NR'R'' 17 and RR''N-NHR' 18 (R = Si(CMe3)Me2, R' = Si(CMe3)2Me, R'' = SiPhF2), while in the reaction of lithiated 6 with (Me2HC)2SiF2 only the tris(silyl)hydrazine RR''N-NHR' 19 is formed . 17-19 are the first silylhydrazines, which are substituted by three different silyl groups.By treating dilithiated 6 with two equivalents SiF4 the tetrakis(silyl)hydrazine R(F3Si)N-(SiF3)R' (R = Si(CMe3)Me2, R' = Si(CMe3)2Me) 20 is formed.The tetrakis(silyl)hydrazine Me3Si(PhF2Si)N-N(SiF2Ph)SiMe3 21 is obtained in the reaction of dilithiated bis(trimethylsilyl)hydrazine with two equivalents PhSiF3.We isolated single crystals of 21 and determined its crystal structure.Two equivalents lithiated 3 react with (CMe3)2SiF2 to give the bis(hydrazino)silane (CMe3)2Si2 22.The reaction of lithiated N,N-dimethylhydrazine with 18 or with N-(trifluorosilyl)-N-(trimethylsilyl)-N',N'-hydrazine leads to the formation of the asymmetric bis(hydrazino)silanes FPhSi (R = Si(CMe3)2Me, R' = Si(CMe3)Me2) 23 and F2Si 24.By treating 24 again with lithiated N,N-dimethylhydrazine the tris(hydrazino)silane 26 is obtained.Finally we discuss the crystal structure of the difluorobissilane 25. - Keywords: silylhydrazines, tert-butylsilylhydrazines, bis- and tris(hydrazino)silanes, crystal structure.
