Cleavage of the Silicon-Silicon and Silicon-Chlorine Bond oftBu₃Si-SiCl₃

Abstract

The reaction of SiCl 4 with Na[SitBu 3 ] in thf at À78 8C yielded tBu 3 Si-SiCl 3 along with tBu 3 SiCl, tBu 3 Si-SitBu 3 , and tBu 3 SiH. After HPLC separation we isolated crystalline tBu 3 Si-SiCl 3 from the eluate (retention time: t = 39 min). During the work-up process further derivatives of tBu 3 Si-SiCl 3 namely tBu 3 Si-Si(OH) 3 (triclinic space group P-1), tBu 3 Si-Si(OMe)(OH) 2 (monoclinic space group P2 1 /c), and tBu 3 Si-Si(OMe) 2 (OH) (monoclinic space group P2 1 /c) crystallize from the eluate. By the reaction of tBu 3 Si-SiCl 3 with K in benzene we obtained the tetrasilatetrahedrane (tBu 3 Si) 4 Si 4 (tetrasupersilyl-tetrahedro-tetrasilane) along with tBu 3 Si-SitBu 3 and tBu 3 SiH. In contrast to the reaction in benzene treatment of tBu 3 Si-SiCl 3 with K in thf yielded K[SitBu 3 ]. We further investigated the cleavage of SiÀSi bond by treatment of tBu 3 Si-SiCl 3 with [nBu 4 N]Cl. Thereby tBu 3 SiCl and [nBu 4 N] 2 [Si 6 Cl 14 ] were formed.

New Aspects with Regard to Silanide Chemistry in Particular Formation and Structure of the First Disilyl Sodate [K(Me2SiO)7][(tBu3Si)2MeSi‐Na‐SiMe(SitBu3)2]

“…Reaction of donor‐free silanide Na[SiMe(Si t Bu 3 ) 2 ] with SiCl 4 (cf. Na[Si t Bu 3 ] and SiCl 4 in reference). (i) –NaCl, –[SiCl 2 ] n , heptane, room temperature.…”