80785-72-4

Upstream product

• 5599-27-9 dichloro(dimesityl)silane 
• 79184-71-7 dimesitylsilylene 
• 79074-00-3 2,4,6-tri-t-butylphenylphosphonous dichloride 
• 74864-45-2 1,1,2,2-tetramesityldisilane 
• 192059-68-0 Mes₂Si(SiMes₂)2 
• 132771-52-9 hexamesitylcyclotrisilane 
• 79184-72-8 2,2-dimesitylhexamethyltrisilane 
• 102780-90-5 2,2-Bis-(2,6-dimethyl-phenyl)-1,1,1,3,3,3-hexamethyl-trisilane 
• 576-83-0 2,4,6-trimethylphenyl bromide 

Downstream Products

• 82545-72-0 C₃₇H₄₈OSi₂ 
• 132068-12-3 2-p-Tolyl-4,4,5,5-tetrakis-(2,4,6-trimethyl-phenyl)-4H,5H-2λ⁴-[1,2,3,4,5]oxathiazadisilole 2-oxide 
• 84537-21-3 4,4-Diphenyl-2,2,3,3-tetrakis-(2,4,6-trimethyl-phenyl)-[1,2,3]oxadisiletane 
• 132093-26-6 N-mesityl-1,2-disila-1,1,2,2-tetramesitylaziridine 
• 132068-15-6 1,4,4,5,5-Pentakis-(2,4,6-trimethyl-phenyl)-4,5-dihydro-1H-[1,2,3,4,5]triazadisilole 
• 132068-11-2 N-(trimethylsilyl)-1,2-disila-1,1,2,2-tetramesitylaziridine 
• 132093-27-7 N-benzyl-1,2-disila-1,1,2,2-tetramesitylaziridine 
• 132068-16-7 N-benzyl-1,2-disila-1,1,2,2-tetramesityltriazene 
• 132068-13-4 2,2-Diphenyl-4,4,5,5-tetrakis-(2,4,6-trimethyl-phenyl)-4,5-dihydro-2λ⁵-[1,3,2,4,5]oxazaphosphadisilole 
• 118376-06-0 4-Phenyl-2,2,5,5-tetrakis-(2,4,6-trimethyl-phenyl)-[1,3,4,2,5]dioxazadisilolidine 
• 118376-05-9 2-Phenyl-3,3,4,4-tetrakis-(2,4,6-trimethyl-phenyl)-[1,2,3,4]oxazadisiletidine 
• 132068-09-8 N-phenyl-1,2-disila-1,1,2,2-tetramesitylaziridine 
• 132068-14-5 N-phenyl-1,2-disila-1,1,2,2-tetramesityltriazoline 
• 132771-55-2 C₃₀H₃₄N₂OSi 

Relevant academic research and scientific papers

Emission from the Excited State of Tetraneopentyldisilene

Fluorescence from tetraneopentyldisilene containing only a silicon-silicon double bond as chromophore is observed with a large Stokes shift (7300 cm-1) in methylcyclohexane-isopentane glass at 77 K.

Addition of S-Heterocyclic Carbenes to Fullerenes: Formation and Characterization of Dithiomethano-Bridged Derivatives

The reactions of novel S-heterocyclic carbenes (SHCs), which were prepared by the cycloaddition of disilenes and digermenes to CS2, with C60 and Sc3N@Ih-C80 afforded the corresponding methano-bridged

Matrix Effect. Dimerization of Silylenes at 77 K in the Matrix

The dimerization of silylenes was studied in hydrocarbon matrix ranging in viscosity from 1E6 to 1E12 at 77 K.The silylenes dimerized to disilenes in soft matrix at 77 K without annealing.

Conformational polymorphism of solid tetramesityldisilene Mes2Si=SiMes2 (Raman, UV-vis, IR and fluorescence study)

Conformational polymorphism of solid tetramesityldisilene (1) has been studied by the methods of optical spectroscopy. The three known modifications of 1: orange unsolvated 1a and two 1:1 solvates with toluene (1b) and THF (1c) have been found to transform under specific conditions to a new, most thermodynamically stable polymorph, yellow unsolvated powder 1d. The latter has been characterized by the Raman, IR, UV-vis and fluorescence data. All forms of 1 exhibit Raman spectra differing in details, which reflect their different crystal and molecular structures. Unsolvated 1a and 1d differ significantly in electronic absorption and fluorescence emission. The yellow form 1d can be converted to the orange form 1a upon illumination with laser light in the region 514-457 nm. Similarity of the Raman and UV-vis spectra of 1d to those of the solutions of 1 provides some evidence for a quasi-trans conformation of 1d.

Reactivity of sulfonyl-containing compounds with ditetrelenes

The addition of a variety of sulfones and a sulfoxide to ditetrelenes (a disilene and a digermene) was examined. The reaction of benzenesulfonyl chloride with tetramesityldisilene or tetramesityldigermene results in the formation of the 1,2-addition products, 2-chlorotetramesityldisilyl- or digermylbenzenesulfinate. The addition of p-toluenesulfonyl chloride to the disilene gave the analogous product, 2-chlorotetramesityldisilyl p-toluenesulfinate. In contrast, benzenesulfonyl fluoride, diphenyl and dimethyl sulfone did not react with either the disilene or the digermene. The unprecedented formation of the sulfinates reveals a selective 2-electron reduction of the sulfur centres using ditetrelenes. The addition reactions of sulfonyl compounds illustrates the potential of ditetrelenes to serve as reducing agents which react rapidly, at room temperature under mild conditions. The reaction of tetramesityldisilene with diphenyl sulfoxide resulted in the formation of tetramesityloxadisilirane and with benzene sulfonic acid resulted in the formation of 1,1,2,2-tetramesityldisilyl benzenesulfonate.

The addition of amides to group 14 (di)-metallenes

The addition of a series of primary and secondary amides to the group 14 (di)metallenes Mes2SiSiMes2, Mes2GeGeMes 2 and (Me3Si)2SiC(OSiMe3)R, where R = t-Bu or R = 1-Ad, was examined. In general, the addition of primary and N-methyl amides gave amide adducts whereas the addition of N-phenyl amides gave imidate adducts. The regiochemistry of the additions was highly dependent upon the substituent bonded to the amide nitrogen. We propose that the formation of the adducts proceeds by way of a zwitterionic intermediate. The reactivity of tetramesityldigermene towards amides is used to predict the structure of the amide adducts formed on the Ge(100)-2 × 1 surface.

Fast kinetics study of the reactions of transient silylenes with alcohols. Direct detection of silylene-alcohol complexes in solution

The kinetic behavior of dimethyl-, diphenyl-, and dimesitylsilylene in hexanes solution in the presence of methanol (MeOH), tert-butanol (t-BuOH), and the respective O-deuterated isotopomers has been studied, with the goal of elucidating a detailed mechanism for the formal O-H insertion reaction of transient silylenes with alcohols in solution. The data are in all cases consistent with a mechanism involving the intermediacy of the corresponding silylene-alcohol Lewis acid-base complexes, which have been detected directly for each of the SiMe2-ROL and SiPh2-ROL (L = H or D) systems that were studied. Complexation proceeds effectively irreversibly (Keq ≥ 2 x 105 M-1) and at close to the diffusion-controlled rate in these cases. In contrast, the kinetic and spectroscopic behavior observed for SiMeS2 in the presence of these alcohols indicates the SiMeS2-ROL complexes are involved as steady-state intermediates, formed reversibly and 10-100 times more slowly than is the case with SiMe2 and SiPh2. Product formation from the silylene-alcohol complexes is shown to proceed via catalytic proton transfer by a second molecule of alcohol, the rate of which exceeds that of unimolecular intracomplex H-migration in all cases, even at submillimolar alcohol concentrations. The catalytic rate constants range from 109 to 1010 M-1 s-1 for the SiMe2-ROH and SiPh2-ROH complexes, sufficiently fast that the isotope effect ranges from ca. 2.5 to close to unity for all but the SiPh2-t-BuOL complex, where it is remarkably large (kHH/kDD = 10.8 ± 2.4). The value is consistent with a mechanism for catalysis involving double proton transfer within a cyclic five-membered transition state. The isotope effects on the ratio of the rate constants for catalytic proton transfer and dissociation of the SiMeS2-MeOH and SiMeS2-t-BuOH complexes suggest that a different mechanism for catalytic proton transfer is involved in the case of the sterically hindered diarylsilylene.

A novel synthesis of tetramesityldisilene

Dimesityldiclorosilane undergoes reductive coupling with potassium-graphite to afford a mixture of cyclic polysilanes in a high yield and purity; this mixture is quantitatively converted to the title compound by photochemical irradiation.

Molecular Interactions of Polysilane and Unsaturated Nitrogen Compounds. Photochemical Addition of Disilene versus Silylene to Azobenzene

Photochemical reaction of hexamesitylcyclotrisilane 1 or tetramesityldisilene 2 with azobenzene produces silanol 5 via hydrolysis of diazasilacyclopropane 3 and/or 1,2-diaza-3,4-disilacyclobutane 4; the structure of 4 has been confirmed by variable temperature 1H NMR spectroscopy and single-crystal X-ray diffraction, the existence of an Si2N2 ring system is demonstrated.

Reactions of tetramesityldisilene with azides: synthesis of disilaaziridines

The reactions of several organic azides (RN3) with tetramesityldisilene (1) were studied.Azides with R = Ph or Mes each gave two products, a disilaaziridine and a disilatriazoline.When R = PhCH2 or Me3SiCH2 intermediate adducts of the azide and the disilene were found.These adducts and the disilatriazolines both react thermally to yield the respective disilaaziridines.For R = Me3Si only a disilaaziridine was observed, the structure of which was determined by X-ray crystallography and was found to have a short Si-Si internuclear distance of 2.23 Angstroem.Crystal data: R = trimethylsilyl, a 23.561(3), b 19.001(3), c 16.916(3) Angstroem, monoclinic, β = 106.095 deg, C2/c, Z = 8.Novel five-membered silicon heterocycles were isolated from the reactions of 1 with toluenesulfonyl azide and diphenylphosphonyl azide.