Premium
A Radical Approach to Hydroxylaminotrichlorosilanes: Synthesis, Reactivity, and Crystal Structure of TEMPO‐SiCl 3 (TEMPO = 2,2,6,6‐Tetramethylpiperidine‐ N ‐oxyl)
Author(s) -
Stefan Spirk,
Belaj Ferdinand,
Madl Tobias,
Pietschnig Rudolf
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200900969
Subject(s) - chemistry , reactivity (psychology) , crystal structure , hydrolysis , radical , silicon , crystal (programming language) , crystallography , stereochemistry , computational chemistry , organic chemistry , computer science , programming language , medicine , alternative medicine , pathology
The reaction of the nitroxy radical 2,2,6,6‐tetramethylpiperidine‐ N ‐oxyl (TEMPO) with SiCl 4 has been investigated in detail. One silicon‐containing product, TEMPO‐SiCl 3 ( 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, 1 decomposes and yields several TEMPO‐containing species. These were all characterized crystallographically.