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Tuning the Anomeric Effect in Sulfamide with Superacids
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2018-10-17 , DOI: 10.1002/chem.201804009 Dominik Leitz 1 , Marie C. Bayer 1 , Yvonne Morgenstern 1 , Florian Zischka 1 , Andreas J. Kornath 1
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2018-10-17 , DOI: 10.1002/chem.201804009 Dominik Leitz 1 , Marie C. Bayer 1 , Yvonne Morgenstern 1 , Florian Zischka 1 , Andreas J. Kornath 1
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This study shows that the anomeric effect (negative hyperconjugation) that arises in sulfamide, as a result of the relatively short S−N bonds, can be tuned by the utilization of superacidic media. Sulfamide was reacted in binary superacidic systems XF/MF5 (M=As, Sb; X=H, D) and HF/BF3. The colorless salts formed, [X2NSO2NX3]+[MF6]− and [H2NSO2NH3]+[BF4]− were characterized by low‐temperature vibrational spectroscopy. In the case of [H2NSO2NH3]+[BF4]−, a single crystal X‐ray diffraction study was performed. The salt crystallizes in the monoclinic space group P21/c with four formula units per unit cell. An exclusive N,N′‐diprotonation was observed in the superacidic system HF/SbF5 when using several equivalents of the Lewis acid. Low‐temperature vibrational spectra as well as a single‐crystal X‐ray structure of [H3NSO2NH3]2+2 [SbF6]−⋅2 HF are reported. The salt crystallizes in the orthorhombic space group Pna21 with four formula units per unit cell. Upon mono‐ or diprotonation of sulfamide, remarkable structural changes of the sulfur–nitrogen bond lengths were observed. Herein, these changes are discussed together with quantum chemical calculations.
中文翻译：
用超强酸调节磺酰胺中的端基作用
这项研究表明，由于相对短的SN键，在磺酰胺中产生的异头作用（负超共轭）可以通过利用超酸性介质来调节。磺酰胺在二元超酸性体系XF / MF 5（M = As，Sb; X = H，D）和HF / BF 3中反应。通过低温振动光谱对形成的无色盐[X 2 NSO 2 NX 3 ] + [MF 6 ] -和[H 2 NSO 2 NH 3 ] + [BF 4 ] -进行表征。在[H 2 NSO 2NH 3 ] + [BF 4 ] -，进行了单晶X射线衍射研究。盐在单斜晶空间群P 2 1 / c中结晶，每个晶胞具有四个分子式单位。当使用数当量的路易斯酸时，在超酸性体系HF / SbF 5中观察到了排他的N，N'-双质子化。低温振动光谱以及的单晶X射线结构[H 3 NSO 2 NH 3 ] 2+ 2的SbF 6 ] - ⋅报告了2 HF。该盐在正交晶空间群Pna 2 1中结晶，每个单元格具有四个公式单位。在磺酰胺单质子化或双质子化时，观察到硫氮键长度的显着结构变化。在此，将这些变化与量子化学计算一起讨论。
更新日期：2018-10-17
中文翻译：
用超强酸调节磺酰胺中的端基作用
这项研究表明，由于相对短的SN键，在磺酰胺中产生的异头作用（负超共轭）可以通过利用超酸性介质来调节。磺酰胺在二元超酸性体系XF / MF 5（M = As，Sb; X = H，D）和HF / BF 3中反应。通过低温振动光谱对形成的无色盐[X 2 NSO 2 NX 3 ] + [MF 6 ] -和[H 2 NSO 2 NH 3 ] + [BF 4 ] -进行表征。在[H 2 NSO 2NH 3 ] + [BF 4 ] -，进行了单晶X射线衍射研究。盐在单斜晶空间群P 2 1 / c中结晶，每个晶胞具有四个分子式单位。当使用数当量的路易斯酸时，在超酸性体系HF / SbF 5中观察到了排他的N，N'-双质子化。低温振动光谱以及的单晶X射线结构[H 3 NSO 2 NH 3 ] 2+ 2的SbF 6 ] - ⋅报告了2 HF。该盐在正交晶空间群Pna 2 1中结晶，每个单元格具有四个公式单位。在磺酰胺单质子化或双质子化时，观察到硫氮键长度的显着结构变化。在此，将这些变化与量子化学计算一起讨论。
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