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三角形全金属芳香配合物从键合困境到强大催化平台的演变

Evolution of Triangular All-Metal Aromatic Complexes from Bonding Quandaries to Powerful Catalytic Platforms.

作者信息

Bigi Franca, Cauzzi Daniele, Della Ca' Nicola, Malacria Max, Maggi Raimondo, Motti Elena, Wang Yanlan, Maestri Giovanni

机构信息

Department of Chemistry, Life Sciences and Environmental Sustainability, Università di Parma, Parco Area delle Scienze 17/A, 43124 Parma, Italy.

IMEM-CNR, Parco Area delle Scienze 37/A, 43124 Parma, Italy.

出版信息

ACS Org Inorg Au. 2022 Aug 12;2(5):373-385. doi: 10.1021/acsorginorgau.2c00029. eCollection 2022 Oct 5.

DOI:10.1021/acsorginorgau.2c00029
PMID:36855666
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9955218/
Abstract

This manuscript describes an overview on the literature detailing the observation of trinuclear complexes that present delocalized metal-metal bonds similar to those of regular aromatics, which are formed combining main group elements. A particular emphasis is given to the structural and electronic features of aromatic clusters that are sufficiently stable to allow their isolation. In parallel to the description of their key bonding properties, the work presents reported catalytic applications of these complexes, which already span from elaborated C-C-forming cascades to highly efficient cross-coupling methods. These examples present peculiar aspects of the unique reactivity exerted by all-metal aromatic complexes, which can often be superior to their established, popular mononuclear peers in terms of chemoselectivity and chemical robustness.

摘要

本手稿概述了文献中对三核配合物的观察,这些配合物呈现出与常规芳烃类似的离域金属-金属键,它们是由主族元素结合形成的。特别强调了芳香族簇合物的结构和电子特征,这些特征足够稳定,可以实现分离。在描述其关键键合性质的同时,该工作还介绍了这些配合物已报道的催化应用,其范围已从精细的碳-碳形成级联反应到高效的交叉偶联方法。这些例子展示了全金属芳香配合物独特反应性的独特方面,在化学选择性和化学稳定性方面,它们通常优于已确立的、流行的单核同类物。

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本文引用的文献

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[{Th(CH)Cl}] is stable but not aromatic.[{Th(CH)Cl}]是稳定的,但不是芳香性的。
Nature. 2022 Mar;603(7902):E18-E20. doi: 10.1038/s41586-021-04319-z. Epub 2022 Mar 23.
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Is Aromaticity a Driving Force in Catalytic Cycles? A Case from the Cycloisomerization of Enynes Catalyzed by All-Metal Aromatic Pd Clusters and Carboxylic Acids.芳香性是催化循环中的驱动力吗?全金属芳香性钯簇和羧酸催化烯炔环异构化的一个实例。
J Phys Chem A. 2021 Nov 25;125(46):10035-10043. doi: 10.1021/acs.jpca.1c07253. Epub 2021 Nov 16.
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Inter/Intramolecular Cascade of 1,6-Enynes Catalyzed by All-Metal Aromatic Tripalladium Complexes and Carboxylic Acids.
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4
Aryl sulfonate anion stabilized aromatic triangular cation [Pd]: syntheses, structures and properties.芳基磺酸根阴离子稳定的芳香族三角阳离子[Pd]:合成、结构与性质
RSC Adv. 2023 Oct 10;13(42):29689-29694. doi: 10.1039/d3ra04460b. eCollection 2023 Oct 4.
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Inorg Chem. 2021 Oct 18;60(20):15101-15105. doi: 10.1021/acs.inorgchem.1c02043. Epub 2021 Sep 24.
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Nature. 2021 Oct;598(7879):72-75. doi: 10.1038/s41586-021-03888-3. Epub 2021 Aug 23.
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7
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