Achternbosch, Moritz and Zibula, Lukas and Kirchhoff, Jan-Lukas and Bauer, Jonathan O. and Strohmann, Carsten (2021) Primary Amine Functionalization of Alkoxysilanes: Synthesis, Selectivity, and Mechanistic Insights. INORGANIC CHEMISTRY, 60 (15). pp. 11562-11568. ISSN 0020-1669, 1520-510X
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We report a highly selective substitution of silicon-bound methoxy groups by primary lithium amides. This unusual reactivity is possible because of the formation of particularly stable lithium methoxide, which compensates for the decreased Si-N bond enthalpy compared to Si-O bonds. In contrast to substitution reactions on halosilanes, highly selective monosubstitutions under mild conditions are possible, even in the presence of further reactive methoxy groups. A combination of experiments and density functional theory calculations was carried out in order to get an extensive understanding of the reaction. The calculations reveal a possible reaction mechanism with considerably low activation barriers and the entry of the nucleophile to be the rate-determining step. The low activation energies allow for the substitutions to be carried out at low temperatures, therefore preventing side reactions from occurring. The presented investigations expand the view of fundamental transformation processes on silicon and give access to a wide variety of functionalized silicon-based building blocks for various fields of chemistry.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | STERIC FACTORS; SILICON; REACTIVITY |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 01 Sep 2022 07:32 |
| Last Modified: | 01 Sep 2022 07:32 |
| URI: | https://pred.uni-regensburg.de/id/eprint/47153 |
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