Isolation and characterization of a triplet nitrene.

IF 19.2 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Nature chemistry Pub Date : 2024-11-19 DOI:10.1038/s41557-024-01669-9

Dongmin Wang, Wang Chen, Haonan Chen, Yizhen Chen, Shengfa Ye, Gengwen Tan

引用次数: 0

Abstract

Nitrene radical compounds are short-lived intermediates in a variety of nitrogen-involved transformations. They feature either a singlet or a triplet ground state, depending on the electronic properties of the substituents. Triplet nitrenes are highly reactive and their isolation in the condensed phase under ambient conditions is challenging. Here we report the synthesis and isolation of a triplet arylnitrene supported by a bulky hydrindacene ligand. The arylnitrene is fully characterized by various spectroscopic and structural techniques including electron paramagnetic resonance spectroscopy and single-crystal X-ray diffraction. Its high stability is largely attributed to the steric hindrance and effective electron delocalization provided by the supporting ligand. Electron paramagnetic resonance spectroscopy in conjunction with highly correlated wavefunction-based ab initio calculations provides support for a triplet ground state nitrene with axial zero-field splitting D = 0.92 cm^-1 and vanishing rhombicity E/D = 0.002.

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三重芘的分离和表征。

芘基化合物是各种涉氮转化过程中的短效中间体。根据取代基的电子特性，它们具有单重基态或三重基态。三重腈具有高活性，在环境条件下的凝聚相中分离三重腈具有挑战性。在此，我们报告了一种由笨重的水合茚配体支持的三重芳基硝基苯烯的合成和分离。通过各种光谱和结构技术，包括电子顺磁共振波谱和单晶 X 射线衍射，对该芳基烯进行了全面表征。它的高稳定性主要归功于支撑配体提供的立体阻碍和有效的电子析出。电子顺磁共振波谱与高度相关的基于波函数的 ab initio 计算相结合，为三重基态腈提供了支持，其轴向零场分裂 D = 0.92 cm-1，菱形度 E/D = 0.002。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Nature chemistry 化学-化学综合

CiteScore

29.60

自引率

1.40%

发文量

226

审稿时长

1.7 months

期刊介绍： Nature Chemistry is a monthly journal that publishes groundbreaking and significant research in all areas of chemistry. It covers traditional subjects such as analytical, inorganic, organic, and physical chemistry, as well as a wide range of other topics including catalysis, computational and theoretical chemistry, and environmental chemistry. The journal also features interdisciplinary research at the interface of chemistry with biology, materials science, nanotechnology, and physics. Manuscripts detailing such multidisciplinary work are encouraged, as long as the central theme pertains to chemistry. Aside from primary research, Nature Chemistry publishes review articles, news and views, research highlights from other journals, commentaries, book reviews, correspondence, and analysis of the broader chemical landscape. It also addresses crucial issues related to education, funding, policy, intellectual property, and the societal impact of chemistry. Nature Chemistry is dedicated to ensuring the highest standards of original research through a fair and rigorous review process. It offers authors maximum visibility for their papers, access to a broad readership, exceptional copy editing and production standards, rapid publication, and independence from academic societies and other vested interests. Overall, Nature Chemistry aims to be the authoritative voice of the global chemical community.