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具有[U(III)与U(I)]之间模糊U氧化状态的封装三角形UCN簇
作者:小柯机器人 发布时间:2021/9/25 19:14:58

苏州大学谌宁团队合成了一种具有[U(III)与U(I)]之间模糊U氧化态的封装三角形UCN簇,(6) -C82 UCN@Cs。相关研究成果于2021年9月23日发表于国际一流学术期刊《美国化学会杂志》。

了解锕系元素的化学行为对于高效管理和使用锕系材料至关重要。

在该研究中,研究人员报道了一个前所未有的UCN簇中氰化物对U的η2(侧向)配位,该簇在C82富勒烯笼中稳定。研究人员成功合成UCN@Cs(6)-C82,并使用质谱、单晶X射线晶体学、循环伏安法、光谱学和理论计算进行了充分表征。键分析表明CN-和铀之间存在显著的捐赠键,以及铀和碳笼之间的共价相互作用。该效应与观察到的延长的氰化物C–N键有关,导致铀的氧化状态在U(III)和U(I)之间表现出模糊性的罕见情况。

氰化铀簇的该前所未有的三角形结构的发现为配位化学提供了新的见解,并突出了铀可能具有的各种各样的成键情况。

附:英文原文

Title: UCN@Cs(6)-C82: An Encapsulated Triangular UCN Cluster with Ambiguous U Oxidation State [U(III) versus U(I)]

Author: Qingyu Meng, Laura Abella, Wei Yang, Yang-Rong Yao, Xinye Liu, Jiaxin Zhuang, Xiaomeng Li, Luis Echegoyen, Jochen Autschbach, Ning Chen

Issue&Volume: September 23, 2021

Abstract: Understanding the chemical behavior of actinide elements is essential for the effective management and use of actinide materials. In this study, we report an unprecedented η2 (side-on) coordination of U by a cyanide in a UCN cluster, which was stabilized inside a C82 fullerene cage. UCN@Cs(6)-C82 was successfully synthesized and fully characterized by mass spectrometry, single crystal X-ray crystallography, cyclic voltammetry, spectroscopy, and theoretical calculations. The bonding analysis demonstrates significant donation bonding between CN– and uranium, and covalent interactions between uranium and the carbon cage. These effects correlate with an observed elongated cyanide C–N bond, resulting in a rare case where the oxidation state of uranium shows ambiguity between U(III) and U(I). The discovery of this unprecedented triangular configuration of the uranium cyanide cluster provides a new insight in coordination chemistry and highlights the large variety of bonding situations that uranium can have.

DOI: 10.1021/jacs.1c07519

Source: https://pubs.acs.org/doi/10.1021/jacs.1c07519

 

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:14.612
官方网址:https://pubs.acs.org/journal/jacsat
投稿链接:https://acsparagonplus.acs.org/psweb/loginForm?code=1000