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

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Abstract

The process of rearrangement of the octadecahydroeicosaborate anion [trans-B20H18]2– → [iso-B20H18]2– in various solvents (acetonitrile, DMF, DMSO) under UV irradiation in dynamics has been studied using 11B NMR spectroscopy. 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, 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 and it has been shown that an increase in the reaction time and an increase in the temperature of the reaction solution is accompanied by degradation of the boron cluster.

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About the authors

O. S. Dontsova

MIREA — Russian Technological University, Institute of Fine Chemical Technologies named after M.V. Lomonosov

Email: avdeeva.varvara@mail.ru
Russian Federation, Moscow, 119571

E. Y. Matveev

MIREA — Russian Technological University, Institute of Fine Chemical Technologies named after M.V. Lomonosov; Kurnakov Institute of General and Inorganic Chemistry

Email: avdeeva.varvara@mail.ru
Russian Federation, Moscow, 119571; Moscow, 119991

E. A. Eshtukova-Shcheglova

MIREA — Russian Technological University, Institute of Fine Chemical Technologies named after M.V. Lomonosov

Email: avdeeva.varvara@mail.ru
Russian Federation, Moscow, 119571

A. I. Nichugovskii

MIREA — Russian Technological University, Institute of Fine Chemical Technologies named after M.V. Lomonosov

Email: avdeeva.varvara@mail.ru
Russian Federation, Moscow, 119571

A. V. Golubev

Kurnakov Institute of General and Inorganic Chemistry

Email: avdeeva.varvara@mail.ru
Russian Federation, Moscow, 119991

V. I. Privalov

Kurnakov Institute of General and Inorganic Chemistry

Email: avdeeva.varvara@mail.ru
Russian Federation, Moscow, 119991

V. V. Avdeeva

Kurnakov Institute of General and Inorganic Chemistry

Author for correspondence.
Email: avdeeva.varvara@mail.ru
Russian Federation, Moscow, 119991

E. A. Malinina

Kurnakov Institute of General and Inorganic Chemistry

Email: avdeeva.varvara@mail.ru
Russian Federation, Moscow, 119991

K. Y. Zhizhin

MIREA — Russian Technological University, Institute of Fine Chemical Technologies named after M.V. Lomonosov; Kurnakov Institute of General and Inorganic Chemistry

Email: avdeeva.varvara@mail.ru
Russian Federation, Moscow, 119571; Moscow, 119991

N. T. Kuznetsov

MIREA — Russian Technological University, Institute of Fine Chemical Technologies named after M.V. Lomonosov; Kurnakov Institute of General and Inorganic Chemistry

Email: avdeeva.varvara@mail.ru
Russian Federation, Moscow, 119571; Moscow, 119991

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Supplementary files

Supplementary Files
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2. Fig. 1. 11B{1H} NMR spectra of a reaction solution demonstrating the process of rearrangement of the [B20H18]2-anion from trans to iso in time to CH3CN.

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3. Fig. 2. 11B{1H} NMR spectra of the reaction solution demonstrating the process of rearrangement of the anion [B20H18]2– from trans to iso in time in DMFA.

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4. Fig. 3. 11B{1H} NMR spectra of the reaction solution demonstrating the process of rearrangement of the anion [B20H18]2- from trans to iso in time in DMSO.

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5. Fig. 4. Graph of the process of transition of the anion [B20H18]2– from the trans isomer to iso.

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6. Fig. 5. 11B{1H} NMR spectra of the reaction solution demonstrating the process of rearrangement of the [B20H18]2- anion from iso to trans with an increase in temperature in DMFA. The signal at +22 m.d., marked *, corresponds to the appearance of borates in the reaction solution.

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7. Scheme 1. Hawthorne rearrangement under UV irradiation.

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8. Scheme 2. Reverse Hawthorne rearrangement under the influence of temperature.

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9. Supplement
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