- F3SiSH and (F3Si)2S: Conflicting observations resolved by unambiguous syntheses
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The reaction between liquid F3SiI and red HgS mainly yields the disilylsulfane (F3Si)2S and, in smaller amounts, hitherto unknown (F3SiS)2SiF2. These fluorosilylsulfanes have different thermal stabilities. (F3Si)2S is a versatile precursor for F3Si derivatives, and at ambient temperature it is stable, while (F3SiS)2SiF2 decomposes rapidly. F3SiSH has been obtained, along with F3SiBr, by selective cleavage of one of the Si-S bonds in (F3Si)2S with HBr in the liquid phase and was for the first time unambiguously characterized. Contrary to previous reports, (F3Si)2O rather than (F2SiS)2 is formed when SiF4 is passed over SiS2 at 1298 K in a quartz tube. Raman and infrared spectra of (F3Si)2S, F3SiSH and its deuterated derivative F3SiSD have been measured and assigned to vibrational fundamentals. Multinuclear NMR spectra have been recorded. Wiley-VCH Verlag GmbH, 2001.
- Beckers, Helmut,Buerger, Hans
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p. 1217 - 1224
(2008/10/08)
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- Difluorosilanethione F2Si=S by flash vacuum thermolysis of (F3Si)2S and by reaction of SiS with F2 - Matrix studies and ab initio calculations
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Difluorosilanethione F2Si=S (1) has been synthesized by Flash Vacuum Pyrolysis of (F3Si)2S at ≥ 500 °C and trapped in an Ar matrix. Furthermore, 1 has been obtained by codeposition of SiS and F2/Ar and by pyrolysis of a matrix-isolated SiS2-XeF2 complex under cryogenic conditions. All six vibrational fundamentals of 1 have been observed in the matrix IR spectrum. Ab initio calculations at the MP2 and CCSD(T) levels using large basis sets have been performed. These calculations have guided the detection of 1 and the vibrational assignment. The best estimate of the structure of 1 with C(2v) symmetry is: r(Si=S) 191.1(1) pm, r(SiF) 156.1(1) pm, angle(FSiF) 103.3(2)°.
- Beckers, Helmut,Breidung, Ju?rgen,Bu?rger, Hans,Ko?ppe, Ralf,Ko?tting, Carsten,Sander, Wolfram,Schno?ckel, Hansgeorg,Thiel, Walter
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p. 2013 - 2019
(2007/10/03)
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