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生成一种瞬态碱稳定的芳基亚铝烯用于芳香族分子的简便解构。

Generation of a transient base-stabilised arylalumylene for the facile deconstruction of aromatic molecules.

作者信息

Dhara Debabrata, Jayaraman Arumugam, Härterich Marcel, Dewhurst Rian D, Braunschweig Holger

机构信息

Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany

Institute for Sustainable Chemistry & Catalysis with Boron, Julius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany.

出版信息

Chem Sci. 2022 May 2;13(19):5631-5638. doi: 10.1039/d2sc01436j. eCollection 2022 May 18.

DOI:10.1039/d2sc01436j
PMID:35694334
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9116349/
Abstract

While a stable base-free arylalumylene bearing a sterically encumbered terphenyl substituent has been reported previously, we herein report that our attempts to form a base-stabilised arylalumylene bearing a relatively small terphenyl substituent and an -heterocyclic carbene base led instead to a "masked" dialumene (LRAl[double bond, length as m-dash]AlRL), self-stabilised by one peripheral aromatic group. Intriguingly, examining the behavior of this species or its transient dialumene formed from reducing the diiodoarylalane in aromatic solvents under different conditions reveals that they both decouple into the desired base-stabilised arylalumylene. This transient acyclic, dicoordinate alumylene is highly reactive, deconstructing benzene and toluene to furnish dialuminium derivatives of pentalene, providing the first example of a neutral Al compound able to deconstruct these less reactive arenes. Computational insights were also gained on the dialumene dissociation and on the mechanism of arene deconstruction by alumylene.

摘要

虽然之前已报道过带有空间位阻三联苯取代基的稳定无碱芳基亚铝烯，但我们在此报告，我们尝试形成带有相对较小三联苯取代基和N - 杂环卡宾碱的碱稳定芳基亚铝烯，却得到了一种由一个外围芳基自稳定的“掩蔽”二铝烯（LRAl═AlRL）。有趣的是，研究该物种或其在不同条件下由还原二碘芳基铝烷在芳族溶剂中形成的瞬态二铝烯的行为发现，它们都会解耦成所需的碱稳定芳基亚铝烯。这种瞬态非环状二配位亚铝烯具有高反应性，能解构苯和甲苯以提供并五苯的二铝衍生物，这是能够解构这些反应性较低芳烃的中性铝化合物的首个实例。还获得了关于二铝烯解离以及亚铝烯解构芳烃机理的计算见解。

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