Synthesis of Wiberg’s Tetrasilatetrahedrane (tBu₃Si)₄Si₄ by a One-Pot Procedure

Abstract

A one-pot synthesis of the tetrasilatetrahedrane (tBu 3 Si) 4 Si 4 was achieved by the reaction of HSiCl 3 and Na[SitBu 3 ]. In this reaction the silane tBu 3 SiH was obtained along with (tBu 3 Si) 4 Si 4 and tBu 3 SiSitBu 3 . The tetrasilatetrahedrane (tBu 3 Si) 4 Si 4 was also obtained via a one-pot approach by treatment of Cl 3 SiSiCl 3 or Cl 3 SiSiCl 2 SiCl 3 with Na-[SitBu 3 ]. In the reaction of HSiCl 3 with Na[SitBu 3 ], two molecules of the tetrasilatetrahedrane (tBu 3 Si) 4 Si 4 crystallize together with one molecule of tBu 3 SiSitBu 3 and one molecule of benzene. Single crystals suitable for X-ray diffraction composed of one molecule of (tBu 3 Si) 4 Si 4 and two molecules of benzene were obtained by recrystallization from benzene.

Branched Hydrosilane Oligomers as Ideal Precursors for Liquid‐Based Silicon‐Film Deposition

“…The formation of isolable amounts of 5 starting from SiCl 4 is remarkable, since the state‐of‐the art educts for the synthesis of neo ‐Si 5 Cl 12 are Si 2 Cl 6 or Si 3 Cl 8 ,. Previously reported related reactions strongly suggest that dichlorosilylene is a likely intermediate in the course of the formation of 5 in the present case. A plausible mechanism responsible for the unexpected formation of 5 is given in Scheme .…”

The Perchlorinated Silanes Si2Cl6 and Si3Cl8 as Sources of SiCl2

“…[6] However, our research group has recently found out that the reaction of 1 with two equivalents of NaA C H T U N G T R E N N U N G [SitBu 3 ] leads to different products. [7,8] Instead of displaying signals for the substitution product (tBu 3 Si)SiCl 2 SiCl 2 A C H T U N G T R E N N U N G (SitBu 3 ), the 29 Si NMR spectrum of the reaction mixture showed resonances resulting from tetrasilatetrahedrane Si 4 A C H T U N G T R E N N U N G (SitBu 3 ) 4 , disilane tBu 3 SiSitBu 3 , chlorosilane tBu 3 SiCl, as well as polychlorosilanes such as neopentasilane 3. [8] Obviously, this implies that a degradation reaction of 1 has taken place, which involves the liberation of SiCl 2 .…”

“…[7,8] Instead of displaying signals for the substitution product (tBu 3 Si)SiCl 2 SiCl 2 A C H T U N G T R E N N U N G (SitBu 3 ), the 29 Si NMR spectrum of the reaction mixture showed resonances resulting from tetrasilatetrahedrane Si 4 A C H T U N G T R E N N U N G (SitBu 3 ) 4 , disilane tBu 3 SiSitBu 3 , chlorosilane tBu 3 SiCl, as well as polychlorosilanes such as neopentasilane 3. [8] Obviously, this implies that a degradation reaction of 1 has taken place, which involves the liberation of SiCl 2 . In this context, we note that 2 reacts with NaA C H T U N G T R E N N U N G [SitBu 3 ] in an analogous manner, yielding the same products as the reaction of 1 with NaA C H T U N G T R E N N U N G [SitBu 3 ].…”

“…It has been known for decades that the SiÀSi bond in haloA C H T U N G T R E N N U N G substituted disilanes can be cleaved in the presence of a Lewis base. The amine-induced disproportionation of perchlorosilanes like Si 2 Cl 6 (1) and Si 3 Cl 8 (2) to quantitatively yield neo-Si 5 Cl 12 (3) and SiCl 4 (Scheme 1) is a particularly intriguing reaction.…”

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

“…Over the past decades, the reaction of Si 2 Cl 6 with amines such as NMe 3 leading to Si(SiCl 3 ) 4 and SiCl 4 has been the subject of numerous studies . Recently, we have repeated the reaction of Si 2 Cl 6 with catalytic amounts of NMe 3 , NMe 2 Et or NEt 3 and found it fully reproducible .…”