Study of the Reversible Hawthorne Rearrangement between Isomeric Forms of the Octadecahydroeicosaborate Anion Using Dynamic 11B NMR Spectroscopy

IF 1.8 3区 化学 Q3 CHEMISTRY, INORGANIC & NUCLEAR Russian Journal of Inorganic Chemistry Pub Date : 2024-03-28 DOI:10.1134/s0036023624600345
O. S. Dontsova, E. Yu. Matveev, E. A. Eshtukova-Shcheglova, A. I. Nichugovskii, A. V. Golubev, V. I. Privalov, V. V. Avdeeva, E. A. Malinina, K. Yu. Zhizhin, N. T. Kuznetsov
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Abstract

The process of rearrangement of the octadecahydroeicosaborate anion [trans-B20H18]2– → [iso-B20H18]2– in organic solvents (acetonitrile, DMF, DMSO) under UV irradiation has been studied using 11B NMR spectroscopy in dynamics. It has been shown that the time of complete isomeric transition depends on the solvent used. In acetonitrile, complete conversion of the [trans-B20H18]2– anion to the iso form is achieved in 1 h; in DMF, the process takes about 2 h; in DMSO, it takes about 3 h. The reverse process of rearrangement of the macropolyhedral borohydride anion [iso-B20H18]2– → [trans-B20H18]2– has been studied under the influence of temperature in DMF; it has been shown that an increase in the reaction time and temperature of the reaction solution is accompanied by degradation of the boron cluster.

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利用动态 11B NMR 光谱研究十八氢硼酸阴离子异构体之间的可逆霍桑重排作用
摘要 使用 11B NMR 光谱动态研究了十八氢硼酸阴离子 [trans-B20H18]2- → [iso-B20H18]2- 在有机溶剂(乙腈、DMF、DMSO)中紫外线照射下的重排过程。研究表明,同分异构体完全转变的时间取决于所使用的溶剂。在乙腈中,[反式-B20H18]2- 阴离子完全转化为异构形式需要 1 小时;在 DMF 中,这一过程需要约 2 小时;在 DMSO 中,则需要约 3 小时。在 DMF 中,研究了温度对大分子硼氢化阴离子 [iso-B20H18]2- → [trans-B20H18]2- 的反向重排过程的影响;结果表明,反应时间和反应溶液温度的增加伴随着硼簇的降解。
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来源期刊
Russian Journal of Inorganic Chemistry
Russian Journal of Inorganic Chemistry 化学-无机化学与核化学
CiteScore
3.10
自引率
38.10%
发文量
237
审稿时长
3 months
期刊介绍: Russian Journal of Inorganic Chemistry is a monthly periodical that covers the following topics of research: the synthesis and properties of inorganic compounds, coordination compounds, physicochemical analysis of inorganic systems, theoretical inorganic chemistry, physical methods of investigation, chemistry of solutions, inorganic materials, and nanomaterials.
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