Ramler Jacqueline, Lichtenberg Crispin
Institute of Inorganic Chemistry, Julius-Maximilians-University Würzburg, Am Hubland, 97074, Würzburg, Germany.
Chemistry. 2020 Aug 12;26(45):10250-10258. doi: 10.1002/chem.202001674. Epub 2020 Jul 28.
Three-coordinate cationic bismuth compounds [Bi(diaryl)(EPMe )][SbF ] have been isolated and fully characterized (diaryl=[(C H ) C H ] , E=S, Se). They represent rare examples of molecular complexes with Bi⋅⋅⋅EPR interactions (R=monoanionic substituent). The P NMR chemical shift of EPMe has been found to be sensitive to the formation of LA⋅⋅⋅EPMe Lewis acid/base interactions (LA=Lewis acid). This corresponds to a modification of the Gutmann-Beckett method and reveals information about the hardness/softness of the Lewis acid under investigation. A series of organobismuth compounds, bismuth halides, and cationic bismuth species have been investigated with this approach and compared to traditional group 13 and cationic group 14 Lewis acids. Especially cationic bismuth species have been shown to be potent soft Lewis acids that may prefer Lewis pair formation with a soft (S/Se-based) rather than a hard (O/N-based) donor. Analytical techniques applied in this work include (heteronuclear) NMR spectroscopy, single-crystal X-ray diffraction analysis, and DFT calculations.
已分离并充分表征了三配位阳离子铋化合物[Bi(diaryl)(EPMe )][SbF ]（二芳基 = [(C H ) C H ] ，E = S，Se）。它们是具有Bi⋅⋅⋅EPR相互作用的分子配合物的罕见例子（R = 单阴离子取代基）。已发现EPMe的 P NMR化学位移对LA⋅⋅⋅EPMe路易斯酸/碱相互作用的形成敏感（LA = 路易斯酸）。这对应于古特曼 - 贝克特方法的改进，并揭示了所研究路易斯酸的硬度/软度信息。已用这种方法研究了一系列有机铋化合物、铋卤化物和阳离子铋物种，并与传统的第13族和阳离子第14族路易斯酸进行了比较。特别是阳离子铋物种已被证明是有效的软路易斯酸，可能更倾向于与软（基于S/Se）而非硬（基于O/N）供体形成路易斯对。这项工作中应用的分析技术包括（异核）NMR光谱、单晶X射线衍射分析和DFT计算。
