5181-43-1

Upstream product

• 5565-32-2 chlorotris(trimethylsilyl)silane 
• 4110-02-5 tris(trimethylsilyl)silyllithium 
• 110-05-4 di-tert-butyl peroxide 
• 1873-77-4 tris-(trimethylsilyl)silane 
• 4098-98-0 tetrakis(trimethylsilyl)silane 
• 3704-48-1 octadeca-methyloctasilane 
• 75-16-1 methylmagnesium bromide 
• 129943-63-1 2-tert-butyl-3-phenyl-1-tris(trimethylsilyl)silyl-1H-phosphirene 
• 80-10-4 diphenylsilyl dichloride 
• 420796-44-7 ((CH₃)3Si)3SiAlI₂C₄H₈O 
• 680-31-9 N,N,N,N,N,N-hexamethylphosphoric triamide 
• 13463-40-6 iron pentacarbonyl 
• 134962-58-6 tris-(trimethylsilyl)silanethiol 
• 7758-95-4 lead(II) chloride 

Downstream Products

• 13058-24-7 tert-butoxytrimethylsilane 

Relevant academic research and scientific papers

Dispersion-energy-driven Wagner-Meerwein rearrangements in oligosilanes

The installation of structural complex oligosilanes from linear starting materials by Lewis acid induced skeletal rearrangement reactions was studied under stable ion conditions. The produced cations were fully characterized by multinuclear NMR spectroscopy at low temperature, and the reaction course was studied by substitution experiments. The results of density functional theory calculations indicate the decisive role of attractive dispersion forces between neighboring trimethylsilyl groups for product formation in these rearrangement reactions. These attractive dispersion interactions control the course of Wagner-Meerwein rearrangements in oligosilanes, in contrast to the classical rearrangement in hydrocarbon systems, which are dominated by electronic substituent effects such as resonance and hyperconjugation.

3,7,10-Trichalcogenaoctasila[3.3.3]propellanes

The reaction of hexakis(trimethylsilyl)disilane with acetyl chloride and aluminum chloride yields hexakis(chlorodimethylsilyl)disilane (5a) under carefully controlled reaction conditions. Treatment of 5a with either H2S/NEt3 or Li2E (E = Se, Te) gives the dodecamethyl-3,7,10-trichalcogenaoctasila[3.3.3]propellanes Si2(SiMe2)6E3 (6a E = S, 6b E = Se, 6c E = Te). The products have been characterized by multinuclear NMR spectroscopy (1H, 13C, 29Si, 77Se, 125Te). The central silicon atoms are very deshielded in comparison with other compounds containing an Si(Si)4 unit due to their incorporation into three five-membered rings. The molecular structures of 5a and 6a are reported revealing an elongated central Si-Si bond in 5a of 2.3865(11) A and three different spatial orientations of the SiMe2Cl groups in each Si(SiMe2Cl)3 unit. In 6a all three five-membered rings Si4S adopt envelope conformations with the four silicon atoms in one plane. A view of the Si8S3 skeleton along the central silicon-silicon bond of 6a resembles a three-blade propeller.

Sterically overcrowded or charge perturbed molecules. XXIII. Hexakis(trimethylsilyl)disilane: structure and photoelectron spectrum of a sterically overcrowded molecule

Hexakis(trimethylsilyl)disilane 3Si-Si3 crystallizes in the rhombohedral space group Rc with six molecules of D3 symmetry per unit cell.The steric overcrowding by the 18 peripheral methyl groups shows up especially in the elongation of the central SiSi bond to 240 pm, in the differing dihedral angles ω(SiSi-SiSi) of 43 deg and 77 deg and in the rather short non-bonded C...C distances of only 352 pm,which reveals an inter-penetration of the methyl groups within their van der Waals radii of about 200 pm.The 1H nuclear magnetic resonance (NMR) spectrum in DCCl3 at 190 K, however, does not exhibit any signal splitting of the 42 equivalent methyl hydrogens and so the rotational barriers must be below 20 kJ mol-1.The photoelectron spectrum shows in its low-energy region between 7.2 eV and 9.3 eV a resolved αSiSi ionization pattern, which can be satisfactorily reproduced by a LCBO-MO model parametrized in terms of the different SiSi/SiSi bond interactions, and the higher ionization energies are assigned on the basis of a radical cation state comparison with 3SiCl, (H3C)3SiCl and (H3C)3CCl.Although the first vertical ionization energy is only 7.70 eV, which is the lowest observed so far a disilane derivative, and in accord with the cyclovoltammetrically determined irreversible first oxidation potential, no persistent radical cation of hexakis(trimethylsilyl)disilane can be generated in solution.

The Sterically Demanding Thiosilyl Group SSi(SiMe3)3as a Ligand in Transition Metal Chemistry

The increasing number of metalloid clusters, synthesized in the last couple of years, gives new insights into the formation process of metals or semi-metals. Metalloid clusters of the transition metals, especially the coinage metals are thereby of particu

Synthesis, characterization and reactivity of yttrium and gadolinium silyl complexes

The syntheses of yttrium and gadolinium-silyl complexes of the form R(Me3Si)2SiMI2(THF)3 (M = Y, Gd; R = Et, SiMe3) through reactions of potassium silyl reagents, KSiR(SiMe3)2(TH

Rearrangement/fragmentation reactions of oligosilanes with aluminum chloride

Reinvestigation of the Lewis acid catalyzed rearrangement of some open-chain permethyloligosilanes with the Al(Fe)Cl3 catalyst system exhibited several cases of additional reactivity: namely, a fragmentation/ cyclization reaction. Introduction of (trimethylsilyl)methyl substituents into the oligosilane substrates strongly facilitated this reaction, yielding cyclic or bicyclic carbacyclosilanes. Investigations concerning the composition of the catalyst system indicated that the incorporation of about 0.1% FeCl3 into the AlCl3 lattice provided an effective catalyst.

Sodium-potassium alloy for the reduction of monoalkylaluminum(III) compounds

Monoalkylaluminum(III) compounds of the type RAIX2 {R = Cp* (C5Me5), X = Cl, Br, I (1-3); (BisAlCl2)2 (Bis = (Me3Si)2CH) (5); TrisSi [(Me3Si)3Si], X = Cl, B

Reaction of tris(trimethylsilyl)silane with pentacarbonyliron

Heating of pentacarbonyliron with tris(trimethylsilyl)silane results in liberation of hydrogen and formation of hexakis(trimethylsilyl)disilane. Photoinitiated reaction of the same compounds begins with oxidative addition of the silicon hydride to the iron complex with liberation of carbon(II) oxide. Subsequent transformations of the adduct lead to formation of bis(trimethylsilyl)silanediyltricarbonylhydrido(trimethylsilyl)iron which can be stabilized as an adduct with hexamethylphosphoramide.

The 1-silyl-1h-phosphirene/1,2-dihydrophosphasilete rearrangement and its preparative significance

Photolysis of the silyl-substituted 1H-phosphirene 3a proceeds selectively with cleavage of a silicon-silicon bond and ring expansion to furnish the 1,2-dihydro-1,2-phosphasilete 4a. The corresponding heterocyclic germanium product, 4b, is prepared analogously from 3b. The preparative significance of 4a is reflected not only in its numerous addition reactions to multiple-bond systems, such as alkynes 8 and 12 and ketene 10, but also in its substitution reactions with the chloro compounds 15, 18, and 21. The latter reactions proceed through the formation of chlorotrimethylsilane and the novel 1,2-dihydro-1,2-phosphasiletes (16, 19, and 22) which, depending on the substitution pattern at the phosphorus atom, undergo various isomerization reactions (16→17, 19→20). The hydrolysis of 4a to 23 by mere traces of water in carefully purified tetrahydrofuran demonstrates the extreme sensitivity of this compound towards moisture.

A new and easy route to polysilanylpotassium compounds

A method is presented for the synthesis of tertiary, secondary, and primary polysilylpotassium compounds. Reaction of potassium tert-butoxide, in either DME or THF, with a suitable precursor molecule, proceeds by cleavage of a trimethylsilyl - polysilanyl bond, and formation of trimethylsilyl tert-butyl ether and a polysilanylpotassium compound. This route allows easy and flexible access to a number of novel polysilanylpotassium compounds, avoiding the hitherto common use of poisonous mercury compounds.