Lehrstuhl für Anorganische Chemie und Strukturchemie and, Centrum für Molekulare Materialen CM2, Fakultät für Chemie, Universität Bielefeld, Universitätsstraße 25, 33615, Bielefeld, Germany.
Chemistry. 2023 Apr 13;29(21):e202203685. doi: 10.1002/chem.202203685. Epub 2023 Mar 9.
The two oxygen-bridged geminal frustrated Lewis pairs (FLP) tBu P-O-AlBis (Bis=CH(SiMe ) ; 1) and tBu P-O-Si(C F ) (2) were reacted with the heterocumulenes PhNCO, PhOCN, PhNCS, CS and PhNSO as well as SO . With isocyanate and cyanate, both 1 and 2, form addition products under formation of five-membered rings. With CS , isothiocyanate and sulfinylaniline, only 1 forms stable adducts, whereas 2 shows reactivity towards sulfinylaniline, but the product decomposed after a few minutes. The reaction of 1 with SO led to partial cleavage of the P-O-Al and Al-C units, as confirmed by X-ray diffraction studies of a complex aggregate. The reaction of 2 with SO affords the 1,2-addition product. All adducts were characterized by means of multinuclear NMR spectroscopy, X-ray crystallography and CHN analyses.
两个氧桥联的双齿受阻路易斯对(tBu P-O-AlBis (Bis=CH(SiMe ) ; 1)和 tBu P-O-Si(C F ) (2))与杂cumulenes PhNCO、PhOCN、PhNCS、CS 和 PhNSO 以及 SO 反应。与异氰酸酯和氰酸盐反应时，1 和 2 都形成五元环的加成产物。与 CS、异硫氰酸酯和亚磺酰苯胺反应时，只有 1 形成稳定的加合物，而 2 对亚磺酰苯胺表现出反应性，但产物在几分钟后分解。X 射线衍射研究证实，1 与 SO 的反应导致 P-O-Al 和 Al-C 单元的部分断裂。2 与 SO 的反应生成 1,2-加成产物。所有加合物均通过多核 NMR 光谱、X 射线晶体学和 CHN 分析进行了表征。
