Author： Niesmann Jörg Klingebiel Uwe Röpken Cord Noltemeyer Mathias Herbst-Irmer Regine
Publisher： Taylor & Francis Ltd
ISSN： 1024-1221
Source： Main Group Chemistry, Vol.2, Iss.4, 1998-10, pp. : 297-308
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Abstract
The iminosilanes (Me 3 C) 2 Si=NR [R=Si(CMe 3 ) 2 C 6 , Si(CHMe 2 )CMe 3 ] react with AlMe 3 to give the monomeric aminodimethylalanes Me 2 Al-N(R)Si(CMe 3 ) 2 Me 1 [R : Si(CMe 3 ) 2 C 6 H 5 ] and 1 [R : Si(CHMe 2 ) 2 CMe 3 ]. The reaction of (Me 3 C) 2 Si=N-Si(CMe 3 ) 2 C 6 H 5 and Me 2 AlCl affords the monomeric aminochloromethylalane ClMeAl-N(R)Si(CMe 3 ) 2 Me 3 [R: Si(CMe 3 ) 2 C 6 H]. The aminofluorosilanes 4 and 7 react with n BuLi in thf under formation of the four-membered litheium ring derivatives (Me 3 C) 2 SiFn(Li(thf) 2 )R 5 [R: Si(ChMe 2 ) 2 Me] and 8 [R:Si(ChMe 3 ) 2 H]. (Me 3 C)SiFn (AlMe 2 ) R 6 [R : Si(ChMe 2 ) 2 Me] is obtained in reaction of the lithium derivative of 4 and Me 2 AlCl in n-hexane 8 and AlCl 3 form the silyliumtrichloroaluminate (Me 3 C) 2 Si =Nr·AlCl 3 9 [R : Si(CMe 3 ) 2 H], 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 grops P2 1 /n, a = 1119.3(1), b = 1560.1(2), c = 1662.2(3) pm, β = 105.75(1)°, V = 2.7936(7) nm 3 , &rgr; calcd = 1.065 mg/m3, Z = 4 and 3392 independent reflections, R1(I > 2&sgr; (I) = 0.035, wr2 (all data)= 0.089, 3 in the space grop P2 1 /n, a = 1115.6(1), b = 1543.8(2), c = 1669.5(2) pm, β = 105.90(1)°, V = 2.7653(5) nm 3 , &rgr; calcd = 1.108 mg/m 3 , Z = 4 and 4908 independent reflections, R1(I > 2&sgr; (I)) = 0.032, wr2 (all data) = 0.088,8 in the space group P2 1 /n,a = 931.2(I), b = 1668.1(2), c = 1950.5(3) pm, β = 97.86(1)° V = 3.0013(7) nm 3 , &rgr; calcd = 1.040 mg/m3, Z = 4 and 3914 independent reflections, R1(I > 2&sgr; (I)) = 0.044, wr2 (all data) = 0.122, and 9 in the space group P2 1 /c, a = 1345.1(2), b = 1001.5(2), c = 1855.1(3) pm, β = 108.61(2)°, V = 2.3684(7) nm 3 , &rgr; calcd = 1.214 mg/m3, Z = 4 and 3080 independent reflections, R1(I > 2&sgr; (I)) = 0.052, wr2(all data) = 0.117.
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