Ruwisch, Lutz M. ; Dürichen, P. ; Riedel, R. (2000)
Synthesis of silyl substituted organoboranes by hydroboration of vinylsilanes.
In: Polyhedron, 19 (3)
Artikel, Bibliographie
Kurzbeschreibung (Abstract)
Hydroboration reactions of dichloroborane-, monochloroborane- and borane-dimethylsulfide with dichloromethylvinylsilane and trichlorovinylsilane were investigated. The proposed structures of the produced organochlorosilylboranes 1–4 were verified by NMR spectroscopic measurements and in the case of [α-(dichloromethylsilyl)ethyl]dichloroborane-dimethylsulfide (4) the molecular structure was determined by single-crystal X-ray diffraction (L.M. Ruwisch, R. Riedel, U. Klingebiel, M. Noltemeyer, Z. Naturforsch., Teil B 54 (1999) 624). Following the Markovnikov rule, the first addition appears strictly regioselective in the α-position to silicon, producing one chiral methine group between silicon and dichloroborane in compound 4. The second addition of borane- or monochloroborane-dimethylsulfide at the vinyl groups of dichloromethylvinylsilane and trichlorovinylsilane also takes place in the α-position to silicon, forming a second chiral methine group. In the case of borane-dimethylsulfide the third addition occurs in the β-position (anti-Markovnikov) owing to steric hindrance to boron in tris[(dichloromethylsilyl)ethyl]borane (1). A stepwise substitution of chlorine bonded at boron in compounds 2 and 3 using hexamethyldisilazane produces bis[α-(dichloromethylsilyl)ethyl]boryl-trimethylsilylamine (5) and bis[α-(trichlorosilyl)ethyl]boryl-trimethylsilylamine (6), respectively, under release of chlorotrimethylsilane. The remaining trimethylsilylamine group in 6 can be replaced by further reaction with 3 forming tetrakis[α-(trichlorosilyl)ethyl]diborylamine (7). This reaction resembles a selective amino condensation at boron. In a similar condensation reaction of 4 with equivalent amounts of hexamethyldisilazane, tris[α-(dichloromethylsilyl)ethyl]borazine (8) can be obtained.
| Typ des Eintrags: | Artikel |
|---|---|
| Erschienen: | 2000 |
| Autor(en): | Ruwisch, Lutz M. ; Dürichen, P. ; Riedel, R. |
| Art des Eintrags: | Bibliographie |
| Titel: | Synthesis of silyl substituted organoboranes by hydroboration of vinylsilanes |
| Sprache: | Englisch |
| Publikationsjahr: | 15 Februar 2000 |
| Verlag: | Elsevier |
| Titel der Zeitschrift, Zeitung oder Schriftenreihe: | Polyhedron |
| Jahrgang/Volume einer Zeitschrift: | 19 |
| (Heft-)Nummer: | 3 |
| Kurzbeschreibung (Abstract): | Hydroboration reactions of dichloroborane-, monochloroborane- and borane-dimethylsulfide with dichloromethylvinylsilane and trichlorovinylsilane were investigated. The proposed structures of the produced organochlorosilylboranes 1–4 were verified by NMR spectroscopic measurements and in the case of [α-(dichloromethylsilyl)ethyl]dichloroborane-dimethylsulfide (4) the molecular structure was determined by single-crystal X-ray diffraction (L.M. Ruwisch, R. Riedel, U. Klingebiel, M. Noltemeyer, Z. Naturforsch., Teil B 54 (1999) 624). Following the Markovnikov rule, the first addition appears strictly regioselective in the α-position to silicon, producing one chiral methine group between silicon and dichloroborane in compound 4. The second addition of borane- or monochloroborane-dimethylsulfide at the vinyl groups of dichloromethylvinylsilane and trichlorovinylsilane also takes place in the α-position to silicon, forming a second chiral methine group. In the case of borane-dimethylsulfide the third addition occurs in the β-position (anti-Markovnikov) owing to steric hindrance to boron in tris[(dichloromethylsilyl)ethyl]borane (1). A stepwise substitution of chlorine bonded at boron in compounds 2 and 3 using hexamethyldisilazane produces bis[α-(dichloromethylsilyl)ethyl]boryl-trimethylsilylamine (5) and bis[α-(trichlorosilyl)ethyl]boryl-trimethylsilylamine (6), respectively, under release of chlorotrimethylsilane. The remaining trimethylsilylamine group in 6 can be replaced by further reaction with 3 forming tetrakis[α-(trichlorosilyl)ethyl]diborylamine (7). This reaction resembles a selective amino condensation at boron. In a similar condensation reaction of 4 with equivalent amounts of hexamethyldisilazane, tris[α-(dichloromethylsilyl)ethyl]borazine (8) can be obtained. |
| Freie Schlagworte: | Hydroboration, Polysilazanes, Precursors, Vinylsilanes, Chloroboranes |
| Fachbereich(e)/-gebiet(e): | 11 Fachbereich Material- und Geowissenschaften 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft 11 Fachbereich Material- und Geowissenschaften > Materialwissenschaft > Fachgebiet Disperse Feststoffe |
| Hinterlegungsdatum: | 19 Nov 2008 15:55 |
| Letzte Änderung: | 20 Feb 2020 13:27 |
| PPN: | |
| Sponsoren: | We gratefully acknowledge financial support of the DFG (Deutsche Forschungsgemeinschaft/Bonn) and the Fonds der Chemischen Industrie (Frankfurt Germany). |
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