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

被引：30

作者：

Stefan, Spirk ^{[1
]}

Belaj, Ferdinand ^{[1
]}

Madl, Tobias ^{[2
]}

Pietschnig, Rudolf ^{[1
]}

机构：

[1] Graz Univ, Dept Chem, A-8010 Graz, Austria

[2] Tech Univ Munich, Dept Chem, D-85747 Garching, Germany

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2010年 / 02期

关键词：

Silicon; Radicals; X-ray diffraction; Reaction mechanisms; Computational chemistry; NITROXIDE; PRECURSORS; COMPLEXES; SILYLENE; TANANE; TEMPO; SET;

D O I：

10.1002/ejic.200900969

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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.

引用

页码：289 / 297

页数：9

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