Yadav Ritu, Sharma Ankita, Das Bindusagar, Majumder Chinmoy, Das Ayantika, Sen Saumik, Kundu Subrata
Department of Chemistry, Indian Institute of Technology Delhi, New Delhi, 110016, India.
Condensed Matter Theory Group, Laboratory for Theoretical and Computational Physics, Center forScientific Computing, Theory, and Data, Paul Scherrer Institute, 5232, Villigen PSI, Switzerland.
Chemistry. 2024 Nov 7;30(62):e202401730. doi: 10.1002/chem.202401730. Epub 2024 Oct 23.
The synthesis and reactivity of an air and water stable Bicyclic (alkyl)(amino)carbene (BICAAC) stabilized phosphenium cation (1) is reported. Air and water stable phosphenium cation are rare in the literature. Compound 1 is obtained by reaction of BICAAC with PhPCl in THF followed by anion exchange with LiOTf. The reduction and oxidation of 1 yielded corresponding α-radical phosphine species (2) and BICAAC stabilized phosphenium oxide (3) respectively. All compounds are well characterized by single crystal X-ray diffraction studies. The Lewis acidity of compounds 1 and 3 are determined by conducting fluoride ion affinity experiments using UV-Vis spectrophotometry and multinuclei NMR spectroscopy. Compounds 1 and 3 exhibited selective binding to fluoride anion but did not interact with other halides (Cl and Br). Quantum chemical calculations were performed to understand the structure and nature of bonding interactions in these compounds, as well as to comprehend the specific bonding affinity to fluoride over other halide ions.
报道了一种空气和水稳定的双环（烷基）（氨基）卡宾（BICAAC）稳定的磷鎓阳离子（1）的合成及反应活性。空气和水稳定的磷鎓阳离子在文献中较为罕见。化合物1通过BICAAC与PhPCl在四氢呋喃中反应，随后与LiOTf进行阴离子交换得到。1的还原和氧化分别产生相应的α-自由基膦物种（2）和BICAAC稳定的氧化磷鎓（3）。所有化合物均通过单晶X射线衍射研究进行了充分表征。使用紫外可见分光光度法和多核核磁共振光谱法通过进行氟离子亲和力实验来测定化合物1和3的路易斯酸度。化合物1和3对氟阴离子表现出选择性结合，但不与其他卤化物（Cl和Br）相互作用。进行了量子化学计算以了解这些化合物中键合相互作用的结构和性质，以及理解对氟相对于其他卤离子的特定键合亲和力。
