氧桥双原子 Al/P 和 Si/P 受阻路易斯酸碱对与杂cumulenes 的反应性。
Reactivity of Oxygen-Bridged Geminal Al/P and Si/P Frustrated Lewis Pairs towards Heterocumulenes.
机构信息
Lehrstuhl für Anorganische Chemie und Strukturchemie and, Centrum für Molekulare Materialen CM2, Fakultät für Chemie, Universität Bielefeld, Universitätsstraße 25, 33615, Bielefeld, Germany.
出版信息
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。
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