Effect of Substituents in the Pentafluorobenzoate and 2,3,4,5- and 2,3,5,6-Tetrafluorobenzoate Anions on the Structure of Cadmium Complexes

IF 16.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Accounts of Chemical Research Pub Date : 2024-05-16 DOI:10.1134/S1070328423601486

M. A. Shmelev, G. A. Razgonyaeva, D. S. Yambulatov, A. G. Starikov, A. A. Sidorov, I. L. Eremenko

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Abstract

New cadmium 2,3,4,5-tetrafluorobenzoate (6HTfb) and 2,3,5,6-tetrafluorobenzoate (4Htfb) complexes, [Cd(6HTfb)(H₂O)₃]_n·(6HTfb)·2nH₂O (I), [Cd₃(Phen)₂(6HTfb)₆] (II, Phen = 1,10-phenanthroline), [Cd₂(Phen)₂(4Htfb)₄]_n·2nH₂O (III), and [Cd(Phen)₂(4Htfb)₂] (IV), were synthesized. Analysis of the obtained results and published data demonstrated that a decrease in the number of fluorine substituents is unfavorable for the formation of coordination polymers comprising stacked alternating fluorinated and non-fluorinated aromatic moieties. In the case of 2,4,5-trifluorobenzoate complex, a typical trivial structure of the binuclear cadmium complex with ligand-shielded metal core is formed. The synthesis of 2,3,4,5- and 2,3,5,6-tetrafluorobenzoate complexes produced an intermediate situation and demonstrated that the structure of complex formation products is affected by not only the number, but also the positions of fluorine substituents. Using quantum chemical calculations, it was shown that the formation of coordination polymers requires a molecular precursor with a Chinese lantern structure stable in solutions, while the formation of unusual flattened binuclear complexes with additionally coordinated water molecules requires doubly bridged binuclear complexes able to switch to a conformation with exposed coordinatively unsaturated metal centers.

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五氟苯甲酸、2,3,4,5- 和 2,3,5,6-Tetrafluorobenzoate 阴离子中的取代基对镉络合物结构的影响

摘要新型 2,3,4,5-四氟苯甲酸镉（6HTfb）和 2,3,5,6-四氟苯甲酸镉（4Htfb）配合物，[Cd(6HTfb)(H2O)3]n-(6HTfb)-2nH2O (I)、合成了[Cd3(Phen)2(6HTfb)6]（II，Phen = 1,10-菲罗啉）、[Cd2(Phen)2(4Htfb)4]n-2nH2O（III）和[Cd(Phen)2(4Htfb)2]（IV）。对所得结果和已发表数据的分析表明，氟取代基数目的减少不利于形成由交替堆叠的含氟和不含氟芳香分子组成的配位聚合物。在 2,4,5-三氟苯甲酸配合物中，形成了典型的双核镉配合物的三元结构，配体屏蔽了金属核心。2,3,4,5- 和 2,3,5,6- 四氟苯甲酸络合物的合成产生了一种中间状态，并证明了络合物形成产物的结构不仅受氟取代基数量的影响，而且还受氟取代基位置的影响。量子化学计算表明，配位聚合物的形成需要具有在溶液中稳定的中国灯笼结构的分子前体，而具有额外配位水分子的不寻常扁平双核络合物的形成则需要双桥双核络合物能够切换到具有暴露的配位不饱和金属中心的构象。

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

Accounts of Chemical Research 化学-化学综合

CiteScore

31.40

自引率

1.10%

发文量

312

审稿时长

2 months

期刊介绍： Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.