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由七配位环胺锚定的三芳氧基配体支撑的前所未有的铀（IV/V）氢氧化物和（IV/V/VI）氧化物配合物对。

Unprecedented pairs of uranium (iv/v) hydroxido and (iv/v/vi) oxido complexes supported by a seven-coordinate cyclen-anchored tris-aryloxide ligand.

作者信息

Löffler Sascha T, Hümmer Julian, Scheurer Andreas, Heinemann Frank W, Meyer Karsten

机构信息

Friedrich-Alexander-Universität Erlangen-Nürnberg (FAU), Department of Chemistry and Pharmacy Inorganic Chemistry Egerlandstraße 1 91058 Erlangen Germany

出版信息

Chem Sci. 2022 Aug 12;13(38):11341-11351. doi: 10.1039/d2sc02736d. eCollection 2022 Oct 5.

DOI:10.1039/d2sc02736d
PMID:36320575
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9533418/
Abstract

We present the synthesis and reactivity of a newly developed, cyclen-based tris-aryloxide ligand precursor, namely cyclen(Me)( ArOH), and its coordination chemistry to uranium. The corresponding uranium(iii) complex [U((OAr )(Me)cyclen)] (1) was characterized by H NMR analysis, CHN elemental analysis and UV/vis/NIR electronic absorption spectroscopy. Since no single-crystals suitable for X-ray diffraction analysis could be obtained from this precursor, 1 was oxidized with methylene chloride or silver fluoride to yield [(cyclen(Me)( ArO))U(X)] (X = Cl (2), F (3)), which were unambiguously characterized and successfully crystallized to gain insight into the molecular structure by single-crystal X-ray diffraction analysis (SC-XRD). Further, the activation of HO and NO by 1 is presented, resulting in the U(iv) complex [(cyclen(Me)( ArO))U(OH)] (4) and the U(v) complex [(cyclen(Me)( ArO))U(O)] (6). Complexes 2, 3, 4, and 6 were characterized by H NMR analysis, CHN elemental analysis, UV/vis/NIR electronic absorption spectroscopy, IR vibrational spectroscopy, and SQUID magnetization measurements as well as cyclic voltammetry. Furthermore, chemical oxidation of 3, 4, and 6 with AgF or AgSbF was achieved leading to complexes [(cyclen(Me)( ArO))U(F)] (5), [(cyclen(Me)( ArO))U(OH)][SbF] (7), and [(cyclen(Me)( ArO))U(O)][SbF] (8). Finally, reduction of 7 with KC yielded a U(iv) complex, spectroscopically and magnetochemically identified as K[(cyclen(Me)( ArO))U(O)].

摘要

我们展示了一种新开发的基于环糊精的三芳氧基配体前体，即环糊精（甲基）（芳氧基）的合成及其与铀的配位化学性质。通过核磁共振氢谱分析、元素分析以及紫外/可见/近红外电子吸收光谱对相应的铀（III）配合物[U((OAr)(Me)环糊精)]（1）进行了表征。由于无法从该前体获得适合X射线衍射分析的单晶，因此用二氯甲烷或氟化银将1氧化，得到[(环糊精（甲基）（芳氧基）)U(X)]（X = Cl（2），F（3）），通过单晶X射线衍射分析（SC-XRD）对其进行了明确表征并成功结晶，以深入了解分子结构。此外，还展示了1对水和一氧化氮的活化作用，生成了铀（IV）配合物[(环糊精（甲基）（芳氧基）)U(OH)]（4）和铀（V）配合物[(环糊精（甲基）（芳氧基）)U(O)]（6）。通过核磁共振氢谱分析、元素分析、紫外/可见/近红外电子吸收光谱、红外振动光谱、超导量子干涉仪磁化测量以及循环伏安法对配合物2、3、4和6进行了表征。此外，用AgF或AgSbF对3、4和6进行化学氧化，得到配合物[(环糊精（甲基）（芳氧基）)U(F)]（5）、[(环糊精（甲基）（芳氧基）)U(OH)][SbF]（7）和[(环糊精（甲基）（芳氧基）)U(O)][SbF]（8）。最后，用KC还原7得到一种铀（IV）配合物，通过光谱和磁化学方法鉴定为K[(环糊精（甲基）（芳氧基）)U(O)]。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/61e9/9533418/9de6d0684383/d2sc02736d-f8.jpg
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