Affiliations: Institute of Inorganic Chemistry, University of GÖttingen, Tammannstr. 4, D-37077 Göttingen, Germany
Note: [] Corresponding author
Note: [] Crystal structure
Note: [] Crystal structure
Abstract: The iminosilanes (Me3C)2Si=NR [R=Si(CMe3)2C6H5,Si(CHMe2)CMe3] react with AlMe3 to give the monomeric aminodimethylalanes Me2Al—N(R)Si(CMe3)2Me 1 [R : Si(CMe3)2 C6H5] and 2 [R : Si(CHMe2)2CMe3]. The reaction of (Me3C)2Si=N—Si(CMe3)2 C6H5 and Me2AlCl affords the monomeric aminochloromethylalane ClMeAl—N(R)Si(CMe3)2Me 3 [R : Si(CMe3)2C6H5]. The aminofluorosilanes 4 and 7 react with nBuLi in thf under formation of the four-membered lithium ring derivatives (Me3C)2SiFN (Li (thf)2)R 5 [R : Si(CHMe2)2Me] and 8 [R : Si(CHMe3)2H]. (Me3C)2SiFN (AIMe2)R 6 [R : Si (CHMe2)2 Me] is obtained in reaction of the lithium derivative of 4 and Me2AlCl in n-hexane. 8 and A1C13 form the silyliumtrichloroaluminate (Me3C)2Si=NR·AlC13 9 [R : Si(CMe3)2H], a four-membered ring with a bridging chlorine atom. The crystal structures of 1, 3, 8 and 9 have been determined. 1 crystallizes in the space groups P21/n, a = 1119.3(1), b = 1560.1(2), c = 1662.2(3) pm, β = 105.75(1)°, V = 2.7936(7) nm3 , ρcalcd = 1.065Mg/m3, Z = 4 and 3392 independent reflections, Rl(I> 2σ(I)) = 0.035, wR2 (all data) = 0.089, 3 in the space group P21/n, a = 1115.6(1), b = 1543.8(2), c = 1669.5(2) pm, β = 105.90(1)°, V= 2.7653(5) nm3 , ρcalcd = 1.108 Mg/m3, Z = 4 and 4908 independent reflections, R1 (I > 2σ(I)) = 0.032, wR2 (all data) = 0.088, 8 in the space group P21/n, a = 931.2(1), b = 1668.1(2), c = 1950.5(3) pm, β = 97.86(1)°, V= 3.0013(7) nm3, ρcalcd= 1.040Mg/m3, Z =4 and 3914 independent reflections, Rl(I > 2σ (I)) = 0.044, wR2 (all data) = 0.122, and 9 in the space group P21/c, a = 1345.1(2), b = 1001.5(2), c = 1855.1(3) pm, β = 108.61(2)°, V= 2.3684(7) nm3, ρcalcd = 1.214 Mg/m3, Z = 4 and 3080 independent reflections, R1 (I > 2 σ (I)) = 0.052, wR2(all data) = 0.117.
