Tris(trimethylsilyl)silyl versus tris(trimethylsilyl)germyl: Radical reactivity and oxidation ability
Lalevée, J; Blanchard, N; Graff, B; Allonas, X; Fouassier, JP
| HERO ID | 611386 |
|---|---|
| In Press | No |
| Year | 2008 |
| Title | Tris(trimethylsilyl)silyl versus tris(trimethylsilyl)germyl: Radical reactivity and oxidation ability |
| Authors | Lalevée, J; Blanchard, N; Graff, B; Allonas, X; Fouassier, JP |
| Journal | Journal of Organometallic Chemistry |
| Volume | 693 |
| Issue | 24 |
| Page Numbers | 3643-3649 |
| Abstract | Abstract: A comparison of the tris(trimethylsilyl)silyl I and tris(trimethylsilyl)germyl II radical reactivity is provided. Their formation as well as their reactivity encountered in a large variety of chemical processes (addition to double bond, halogen abstraction, peroxyl radical formation…) is examined by laser flash photolysis, quantum mechanical calculations and electron spin resonance (ESR) experiments. The starting compound (TMS)3GeH is more reactive than (TMS)3SiH toward the t-butoxyl, the t-butylperoxyl and the phosphinoyl radicals. A similar behavior is noted for an aromatic ketone triplet state. II exhibits a lower absolute electronegativity: accordingly, the addition to electron rich alkenes is less efficient than for I. Radical II is also found less reactive for both the peroxylation and the halogen abstraction reactions. The rearrangement of is slower than for ; this is related to the respective exothermicity of the processes. [Copyright 2008 Elsevier] Copyright of Journal of Organometallic Chemistry is the property of Elsevier Science Publishers B.V. and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts) |
| Doi | 10.1016/j.jorganchem.2008.08.039 |
| Wosid | WOS:000260309900014 |
| Is Certified Translation | No |
| Dupe Override | No |
| Is Public | Yes |
| Keyword | RADICALS (Chemistry); CHEMICAL processes; OXIDATION; REACTIVITY (Chemistry); ELECTRON paramagnetic resonance; FLASH photolysis |
| Is Qa | No |