Sb-to-P Metathesis - 结构受限阳离子 PIII 化合物的直接途径

IF 16.1 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Angewandte Chemie International Edition Pub Date : 2024-11-21 DOI:10.1002/anie.202419772

Roman Dobrovetsky, Deependra Bawari, Irina Malahov

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引用次数: 0

摘要

通过 PCl3 和 LSb-Cl 之间的 Sb-to-P 偏合成反应，直接合成了结构受限的阳离子 PIII 化合物 [LP][SbCl4]，该化合物具有一个中心碳烯供体的 OCO 钳子型配体（L）。分离出[LP][SbCl4]，并研究了它与小分子（ROH 和 RNH2）的反应性，结果表明[SbCl4]- 并非一个无辜的反阴离子，而是这些反应的积极参与者。当用[CB11H12]-（[Cb]-）阴离子取代[SbCl4]-时，反应只转向[LP]+阳离子。与醇类和胺类的反应导致了 P 中心正式 E-H（E = O、N）键氧化加成产物与 P 中心/配体辅助键活化产物之间的平衡。值得注意的是，[LP]+ 能以可逆的热中性方式活化 PhO-H 和 PhN(H)-H 键。

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Sb-to-P Metathesis - A Direct Route to Structurally Constrained, Cationic PIII Compound

Structurally constrained, cationic PIII compound [LP][SbCl4] with an OCO pincer-type ligand (L) having a central carbene donor was directly synthesized via an Sb-to-P metathesis reaction between PCl3 and LSb-Cl. [LP][SbCl4] was isolated and its reactivity with small molecules (ROH and RNH2) was studied, showing that [SbCl4]– is not an innocent counter anion, but an active participant in these reactions. When the [SbCl4]– was replaced with the [CB11H12]– ([Cb]–) anion, the reactions were redirected to [LP]+ cation only. The reactions with alcohols and amines led to the equilibrium between the products of the formal E−H (E = O, N) bond oxidative addition to the P-center and products of the P-center/ligand-assisted bond activation. Remarkably, [LP]+ activated the PhO−H and PhN(H)−H bonds in a reversible, thermoneutral fashion.

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来源期刊

Angewandte Chemie International Edition 化学-化学综合

CiteScore

26.60

自引率

6.60%

发文量

3549

审稿时长

1.5 months

期刊介绍： Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.