- Formation and Identification of Bistri- and tetrachalcogenides
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The reaction of (Me3Si)2NLi aith SCl2 and elemental sulfur or with Se2Cl2 and elemental selenium leads to the formation of mixtures of bissulfides and selenides 2Ex (E = S or Se; x = 1-4).The reaction products were identified by mass spectroscopy as well as by 77Se and 13C NMR spectroscopy.The reaction of (Me3Si)2NH with S2Cl2 produces 2S3 as the main product with only traces of other aminosulfides. 2S3 was purified by distillation under reduced pressure and identified by elemental analysis, mass spectroscopy, and by 1H, 13C, and 14N NMR spectroscopy.The successful cyclocondensation reaction of 2S3 with SCl2 and SO2Cl2 produces S4N2 in 72percent yield and provides further verification of the identity of bistrisulfide.While the analogous reaction of (Me3Si)2NH with Se2Cl2 also leads to the formation of 2Se3 (48 mol percent) as the main product, the reaction mixture contains 2Se2 and 2Se4 in significant amounts (17 and 35 mol percent, respectively).Attempts to purify the mixture by distillation under reduced pressure resulted only in the formation of a 83:17 mixture of 2Se2 and 2Se3. - Keywords: Bissulfides; Bisselenides; Tetrasulfur Dinitride; NMR Spectra; Mass Spectra
- Siivari, Jari,Maaninen, Arto,Haapaniemi, Esa,Laitinen, Risto S.,Chivers, Tristram
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p. 1575 - 1582
(2007/10/03)
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- Polysulfonylamines, XXI. Bis(dimesylamino)sulfane and Bis(dimesylamino)disulfane: Preparation, Properties and Solid State Structures
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High yield syntheses of the new diaminosulfanes (CH3SO2)2NSN(SO2CH3)2 (1) and (CH3SO2)2NSSN(SO2CH3)2 (2) are reported. 1 is obtained by the action of elemental sulfur on (CH3SO2)2NCl and by metathesis of (CH3SO2)2NAg with SCl2, 2 by the analogous metathesis with S2Cl2. 2 is converted to 1 by partial desulfurization with (C6H5)3P. 1 and 2 are active transfer reagents of the S2+ or S22+ group, respectively.Thus, the reaction of 1 or 2 with n-butanol gives the alkoxysulfanes C4H9OSnOC4H9 (n = 1, 2), and their reaction with 2NH leads to the silylated diaminosulfanes 2NSnN2 (n = 1, 2).The crystal structures of the title compounds were determined at -95 deg C.The most important features of the structure of 1 are the near planarity of the three bonds around the nitrogen atoms (sum of bond angles 356.9 deg), the distances N-SII 169.7 and N-SVI 171.5 pm, and the N-SII-N bond angle of 105.3 deg (mean values for two independent molecules).In 2, both nitrogen atoms have a planar geometry (sum of bond angles 360.0 deg; distance from the plane of their bonded atoms 2 pm).All N-S bond lengths are approximately equal (mean values: N-SII 170.4, N-SVI 170.7 pm).The S-S bond length is 202.1 pm.The torsion angle N-S-S-N of -85 deg lies in the usual range for disulfides X-S-S-Y.For comparison, the known structure of CH3-N(SO2CH3)2 was redetermined at -95 deg C.
- Blaschette, Armand,Naeveke, Martina,Jones, Peter G.
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