Department of Chemistry, Ludwig-Maximilian University of Munich, Butenandtstr. 5-13, 81377, München, Germany.
ChemistryOpen. 2021 Jan;10(1):8-15. doi: 10.1002/open.202000220. Epub 2020 Dec 17.
γ-Butyrolactone and γ-butyrolactam were reacted in the superacidic systems XF/MF (X=H, D; M=As, Sb). Salts of the monoprotonated species of γ-butyrolactone were obtained in terms of [(CH ) OCOH] [AsF ] , [(CH ) OCOH] [SbF ] and [(CH ) OCOD] [AsF ] and the analogous lactam salts in terms of [(CH ) NHCOH] [AsF ] , [(CH ) NHCOH] [SbF ] and [(CH ) NDCOD] [AsF ] . The salts were characterized by low temperature Raman and infrared spectroscopy and for both protonated hexafluoridoarsenates, [(CH ) OCOH] [AsF ] and [(CH ) NHCOH] [AsF ] , single-crystal X-ray structure analyses were conducted. In addition to the experimental results, quantum chemical calculations were performed on the B3LYP/aug-cc-pVTZ level of theory. As in both crystal structures C⋅⋅⋅F contacts were observed, the nature of these contacts is discussed with Mapped Electrostatic Potential as a rate of strength.
γ-丁内酯和γ-丁内酰胺在超强酸性体系 XF/MF（X=H，D；M=As，Sb）中反应。根据[(CH ) OCOH] [AsF ]、[(CH ) OCOH] [SbF ]和[(CH ) OCOD] [AsF ]得到了γ-丁内酯单质子化物种的盐，根据[(CH ) NHCOH] [AsF ]、[(CH ) NHCOH] [SbF ]和[(CH ) NDCOD] [AsF ]得到了类似的内酰胺盐。盐通过低温拉曼和红外光谱进行了表征，对于两种六氟代砷酸的质子化盐[(CH ) OCOH] [AsF ]和[(CH ) NHCOH] [AsF ]，进行了单晶 X 射线结构分析。除了实验结果，还在 B3LYP/aug-cc-pVTZ 理论水平上进行了量子化学计算。由于在这两种晶体结构中都观察到了 C⋅⋅⋅F 接触，因此用静电势映射讨论了这些接触的性质，作为强度的速率。
