ChemInform Abstract: Unexpected Disproportionation of Tetramethylethylenediamine‐Supported Perchlorodisilane Cl₃SiSiCl₃.

Abstract

Unexpected Disproportionation of Tetramethylethylenediamine-Supported Perchlorodisilane Cl3SiSiCl3. -Reactions of (I) with tetramethylethylenediamine are studied and the crystal structures of (II), (III), (IV), and (VI) are determined by single crystal XRD. Compounds (II) and (IV) crystallize in the monoclinic space group P21/n with Z = 4, (III) in the monoclinic space group P21/n with Z = 2, and (VI) in the monoclinic space group Cc with Z = 16. The crystal structure of (II) displays one tetrahedrally and one octahedrally bonded Si atom. -(TILLMANN, J.; MEYER-WEGNER, F.; NADJ, A.; BECKER-BALDUS, J.; SINKE, T.; BOLTE, M.; HOLTHAUSEN, M. C.; WAGNER, M.; LERNER*, H.-W.; Inorg. Chem. 51 (2012) 15, 8599-8606, http://dx.

Trapping Experiments on a Trichlorosilanide Anion: a Key Intermediate of Halogenosilane Chemistry

“…A corresponding synthesis was subsequently carried out SiBI 3 ] precluded its characterization by solution-phase NMR spectroscopy. Solid-state magicangle-spinning NMR spectroscopy also did not provide interpretable data, likely because the 29 Si NMR resonance is severely broadened due to coupling with the 10 B and 11 B nuclei (S = 3 and 3 / 2 , respectively). The quadrupolar nature of the boron nuclei leads to a further broadening of the 29 Si NMR signal and also affects the resolution of the 11 and silicon [3.51% (3.02%)].…”

“…38 After 1 equiv of neat Si 2 Cl 6 had been added at room temperature, an exothermic reaction occurred, but the visual appearance of the mixture remained essentially the same. The sample was vacuum-sealed and investigated by 11 B and 29 Si NMR spectroscopy. The 11 B NMR spectrum showed only one resonance, which was assignable to the [BCl 4 ] − ion (δ = 6.6).…”

“…As a downside of this approach, two types of halogen atoms are now present in the sample such that various mixed-halogen species are likely to be formed. Indeed, an 11 B NMR spectroscopic investigation of the sample revealed the presence of all five possible tetrahalogenoborate anions [BCl n I 4−n ] − (n = 0−4), and the corresponding 29 Si NMR spectrum contained the signals of SiCl 4 and SiCl 3 I (see the Supporting Information for more details). The NMR tube was stored at room temperature in the dark in order to avoid photolysis of iodoborane species.…”

Donor–Acceptor Stabilized Tetra(silanimine)

“…are shorter than those in 1 (Si-Namido: 1.769 (7), Si-Namidinate: 1.8780(10), 1.8776(10) Å), respectively. On the basis of the 29 Si NMR resonances and Si-N bond lengths, compound 3 comprises a cationic silicon centre (Si1). analysed by X-ray crystallography.…”

Decachlorocyclopentasilanes coordinated by pairs of chloride anions, with different cations, but the same solvent molecules

“…In the recent years, new and facile synthetic protocols for the Cl À diadduct [Si 6 Cl 14 ] 2of dodecachlorocyclohexasilane have been developed. It can either be prepared through the chloride-induced disproportionation of Si 2 Cl 6 , which leads directly to [Si 6 Cl 14 ] 2- (Tillmann et al, 2012(Tillmann et al, , 2014Tillmann, Moxter et al, 2015), or the Lewis acidic uncomplexed Si 6 Cl 12 can be used as the starting material. In the latter case, mere addition of soluble chloride salts [R 4 N]Cl (R = nBu or Et) leads to the formation of [Si 6 Cl 14 ] 2- (Dai et al, 2010).…”