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在重金属阴离子团簇[Th@Bi12]4-中实现超强π-芳香性
作者:小柯机器人 发布时间:2020/12/11 13:52:25

德国马尔堡大学的Stefanie Dehnen研究组经过不懈努力,在一种重金属阴离子团簇[Th@Bi12]4-中实现了超强π芳香性。这一研究成果于2020年12月7日发表在国际顶尖学术期刊《自然·化学》上。

该课题组提出了一种金属12元环的简单合成方法,该环具有2π芳香性,并且其环电流比苯(6π)强得多,几乎与卟吩(26π)相当,而这些有机分子所含的π电子数却多得多。高度还原的反应条件使得异金属阴离子[Th@Bi12]4-得以成功制备,其间的Th4+稳定着Bi128-基团。这项研究结果表明,在大的金属环中设计和产生强π芳香性是可行的,而这也为π芳香性重金属环在基于团簇的反应中的应用提供了可能。

据了解,芳香性的概念最初是从像苯环这样的不饱和环状平面有机分子中定义的,这一类分子通过内部4n+2个π电子在环上的离域化得以增强稳定性。自那以后,π芳香性在许多有机和无机非金属化合物中都被发现,但之前尚未在只含金属原子的分子中被观察到。

附:英文原文

Title: Substantial π -aromaticity in the anionic heavy-metal cluster [Th@Bi 12 ] 4−

Author: Armin R. Eulenstein, Yannick J. Franzke, Niels Lichtenberger, Robert J. Wilson, H. Lars Deubner, Florian Kraus, Rodolphe Clrac, Florian Weigend, Stefanie Dehnen

Issue&Volume: 2020-12-07

Abstract: The concept of aromaticity was originally defined as a property of unsaturated, cyclic planar organic molecules like benzene, which gain stability by the inherent delocalization of 4n+2 π-electrons over the ring atoms. Since then, π-aromaticity has been observed for a large variety of organic and inorganic non-metal compounds, yet, for molecules consisting only of metal atoms, it has remained restricted to systems with three to five atoms. Here, we present the straightforward synthesis of a metal 12-ring that exhibits 2π-aromaticity and has a ring current much stronger than that of benzene (6π) and equivalent to that of porphine (26π), despite these organic molecules having (much) larger numbers of π-electrons. Highly reducing reaction conditions allowed access to the heterometallic anion [Th@Bi12]4, with interstitial Th4+ stabilizing a Bi128 moiety. Our results show that it is possible to design and generate substantial π-aromaticity in large metal rings, and we hope that such π-aromatic heavy-metal cycles will eventually find use in cluster-based reactions.

DOI: 10.1038/s41557-020-00592-z

Source: https://www.nature.com/articles/s41557-020-00592-z

 

期刊信息

Nature Chemistry:《自然—化学》,创刊于2009年。隶属于施普林格·自然出版集团,最新IF:21.687
官方网址:https://www.nature.com/nchem/
投稿链接:https://mts-nchem.nature.com/cgi-bin/main.plex