Preparation of tris(trimethylsilyl)methyl (“trisyl”) derivatives of silicon

Synthesis and reactions of [tris(trimethylsilyl)methyl]ethyl dichlorosilane

“…The 400 MHz NMR spectra of most of our compounds gave non-first-order ethyl resonances, as found previously for compounds TsiSiEt 2 X and TsiSiEtMeX [16,17], but in those for TsiSiEtX 2 (X = I, OH, SCN, N 3 ) and TsiSiEtIOMe the CH 3 and CH 2 resonances were clearly resolved.…”

“…The hydride TsiSiEtH 2 has been reacted with two equivalent of Br 2 in CCl 4 to give the corresponding dibromide. The reaction of TsiSiEtH 2 with Br 2 or ICl (uncatalized by light) in CCl 4 is fast, and occurs with retention [17]. For the compounds of the type TsiSiR 2 X with R = Me or Ph, X = F, Cl, Br, I, there is no reaction with methanol alone, but with sodium methoxide in methanol fragmentation occurs (presumably driven by release of steric strain) to give products of the type (Me 3 Si) 2 CHSiR 2 OMe, seemingly via the silaolefins (Me 3 Si) 2 C = SiR 2 [11].…”

Synthesis, Characterization, and Reactivity of [LiC(SiMe2H)3]·2THF: Formation of 1,1,3,3-Tetramethyl-2,2,4,4-tetrakis(dimethylsilyl)- 1,3-disilacyclobutane, [Me2SiC(SiMe2H)2]2

“…Substitution of both chlorine atoms did not occur when an excess of 1 was employed in the reaction (Scheme ), indicative of a large steric hindrance by the (HMe 2 Si) 3 C group to substitution at silicon. Analogous results were reported by Eaborn for reactions between [LiC(SiMe 3 ) 3 ] and halosilanes . The reactions between 1 and 1 equiv of HSiCl 3 or MeSiCl 3 in THF at −78 °C produced air- and moisture-stable solids, Cl 2 HSiC(SiMe 2 H) 3 ( 4 ) and (Cl 2 MeSi)C(SiMe 2 H) 3 ( 5 ), respectively (eq 2).…”

NHC-Stabilized Silicon–Carbon Mixed Cumulene

“…The silene (Me 3 Si) 2 CSiCl­(SiMe 3 )­(IPr) ( 2 ) was synthesized in ca. 40% yield by the reduction of (Me 3 Si) 3 CSiCl 3 ( 1 ) with lithium naphthalenide (LiNp) in the presence of IPr (Scheme ). It has been reported that the similar reduction of 1 in the absence of NHCs yielded the corresponding silylenoid (Me 3 Si) 3 CSiCl 2 (Li) .…”