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Stefan, S; Belaj, F; Madl, T; Pietschnig, R.
A Radical Approach to Hydroxylaminotrichlorosilanes: Synthesis, Reactivity, and Crystal Structure of TEMPO-SiCl3 (TEMPO=2,2,6,6-Tetramethylpiperidine-N-oxyl)
EUR J INORG CHEM. 2010; (2): 289-297. Doi: 10.1002/ejic.200900969
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Co-authors Med Uni Graz: Madl Tobias
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Abstract:: The reaction of the nitroxy radical 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) with SiCl4 has been investigated in detail. One silicon-containing product, TEMPO-SiCl3 (1), could be isolated in crystalline form, and its crystal structure was determined. The structural parameters have been compared with the related hydroxylaminotrichlorosilane known from the literature and with DFT calculations. According to the calculations, the formation of 1 follows an S(N)2 mechanism, which is thermodynamically favored over an S(N)1 pathway. Upon hydrolysis, I decomposes and yields several TEMPO-containing species. These were all characterized crystallographically.
Find related publications in this database (Keywords): Silicon; Radicals; X-ray diffraction; Reaction mechanisms; Computational chemistry