Journal article
A Radical Approach to Hydroxylaminotrichlorosilanes: Synthesis, Reactivity, and Crystal Structure of TEMPO-SiCl3 (TEMPO = 2,2,6,6-Tetramethylpiperidine-N-oxyl).



Publication Details
Authors:
Spirk, S.; Belaj, F.; Madl, T.; Pietschnig, R.
Publisher:
Wiley-VCH Verlag GmbH & Co. KGaADO - 10.1002/ejic.200900969
Publication year:
2010
Journal:
European Journal of Inorganic Chemistry
Pages range:
289-297
Start page:
289
End page:
297
ISSN:
1434-1948

Abstract
The reaction of the nitroxy radical 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) with SiCl4 has been investigated in detail. One silicon-contg. product, TEMPO-SiCl3 (1), could be isolated in cryst. form, and its crystal structure was detd. The structural parameters have been compared with the related hydroxylaminotrichlorosilane known from the literature and with DFT calcns. According to the calcns., the formation of 1 follows an SN2 mechanism, which is thermodynamically favored over an SN1 pathway. Upon hydrolysis, 1 decomps. and yields several TEMPO-contg. species. These were all characterized crystallog. [on SciFinder(R)]


Keywords
radical hydroxylaminotrichlorosilane prepn reactivity crystal structure TEMPO silyltrichloride DFT


Authors/Editors

Last updated on 2019-25-07 at 16:05