铝钠和铝钾对苯的 1,4-二重发亮作用

IF 2.4 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Polyhedron Pub Date : 2024-09-17 DOI:10.1016/j.poly.2024.117226

Andrea O’Reilly , Andrew M.S. Booth , Claire L. McMullin , J. Robin Fulton , Martyn P. Coles

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引用次数: 0

摘要

在强制条件下，铝[AM{Al(NON)}]2（[NON]2- = [O(SiMe2NDipp)2]2-, Dipp = 2,6-iPr2C6H3, AM = Na, K）与苯反应，生成 1,4- 苯二（氢化物）铝酸盐络合物 AM2[1,4-{Al(NON)(H)}2(C6H4)]。产物的晶体结构分析表明，"Al(NON)(H) "基团位于对位取代的 C6 环的平面上，上方和下方的碱金属形成了反三明治结构。密度泛函理论计算分析了生成二取代产物的机理。结果发现了一种可行的二聚途径，并表明每个矾化步骤之前都有一个迈森海默型中间体，从而导致观察到的反式二矾化产物。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

1,4-Dialumination of benzene by sodium and potassium aluminyls

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1,4-Dialumination of benzene by sodium and potassium aluminyls

Under forcing conditions, the aluminyls [AM{Al(NON)}]₂ ([NON]²⁻ = [O(SiMe₂NDipp)₂]²⁻, Dipp = 2,6-iPr₂C₆H₃, AM = Na, K) react with benzene to give the 1,4-phenylene di(hydrido)aluminate complexes, AM₂[1,4-{Al(NON)(H)}₂(C₆H₄)]. Crystal structure analysis of the products shows that the ’Al(NON)(H)’ groups are in the plane of the para-substituted C₆-ring, with the alkali metals above and below forming an inverse sandwich structure. Density functional theory calculations were performed to analyse the mechanism leading to the di-substituted product. Results identify a viable dimeric pathway and show that each alumination step is preceded by a Meisenheimer-type intermediate leading to the observed trans-dialuminated product.

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来源期刊

Polyhedron 化学-晶体学

CiteScore

4.90

自引率

7.70%

发文量

515

审稿时长

2 months

期刊介绍： Polyhedron publishes original, fundamental, experimental and theoretical work of the highest quality in all the major areas of inorganic chemistry. This includes synthetic chemistry, coordination chemistry, organometallic chemistry, bioinorganic chemistry, and solid-state and materials chemistry. Papers should be significant pieces of work, and all new compounds must be appropriately characterized. The inclusion of single-crystal X-ray structural data is strongly encouraged, but papers reporting only the X-ray structure determination of a single compound will usually not be considered. Papers on solid-state or materials chemistry will be expected to have a significant molecular chemistry component (such as the synthesis and characterization of the molecular precursors and/or a systematic study of the use of different precursors or reaction conditions) or demonstrate a cutting-edge application (for example inorganic materials for energy applications). Papers dealing only with stability constants are not considered.