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有机一氧化硼自由基
作者:小柯机器人 发布时间:2026/1/23 17:06:39


近日,复旦大学李振华团队制备了有机一氧化硼自由基。相关论文发表在2026年1月21日出版的《美国化学会志》上。

一氧化硼自由基作为一种引人注目的分子和短寿命中间体,此前仅在基质隔离条件下被观测到。

研究组报道了通过二硼(6)双阴离子与一氧化氮反应,成功合成并表征了一种稳定的有机一氧化硼自由基。该氧中心自由基通过三芳基取代的硼基基团实现独特的功能化和稳定化。研究组采用电子顺磁共振波谱、单晶X射线衍射分析等多种光谱与结构技术对其进行了全面表征。值得注意的是,该氧中心自由基可被钾阳离子稳定,在氩气氛围下于室温表现出显著稳定性,即使受热或紫外光照射也不会发生自二聚。然而当钾阳离子被完全封装时,它能二聚形成过氧化物物种。此外,该自由基还能通过介导一氧化氮偶联生成硼基连二次硝酸盐衍生物,从而模拟过渡金属配合物的行为。最终,该一氧化硼自由基在锡-锡偶联反应中也展现出良好的催化潜力。

附:英文原文

Title: An Organoborate Monoxide Radical

Author: Shuchang Li, Gan Xu, Yong Luo, Zhen Hua Li, Zhenpin Lu

Issue&Volume: January 21, 2026

Abstract: The boron monoxide radical has emerged as a fascinating molecule and a short-lived intermediate, previously observed only under matrix isolation conditions. In this study, we report the successful synthesis and characterization of a stable organic boron monoxide radical, achieved through the reaction of a diboron (6) dianion with nitric oxide (NO). This oxygen-centered radical is uniquely functionalized and stabilized by a triaryl-substituted boryl group. Comprehensive characterization was performed using various spectroscopic and structural techniques, including electron paramagnetic resonance (EPR) spectroscopy and single-crystal X-ray diffraction analysis. Remarkably, this oxygen-centered radical is stabilized by the K cation and exhibits significant stability under argon at room temperature, showing no self-dimerization even when heated or exposed to UV light. However, it can dimerize to form peroxide species when the K cation is fully encapsulated. Furthermore, it can mimic transition-metal complexes by mediating NO coupling to form a boryl hyponitrite (N2O22–) derivative. Finally, this boron monoxide radical also shows promising catalytic potential in Sn–Sn coupling reactions.

DOI: 10.1021/jacs.5c20813

Source: https://pubs.acs.org/doi/full/10.1021/jacs.5c20813

期刊信息

JACS:《美国化学会志》,创刊于1879年。隶属于美国化学会,最新IF:16.383
官方网址:https://pubs.acs.org/journal/jacsat
投稿链接:https://acsparagonplus.acs.org/psweb/loginForm?code=1000