danДоклады Национальной академии наук БеларусиDoklady of the National Academy of Sciences of Belarus1561-83232524-2431The Republican Unitary Enterprise Publishing House "Belaruskaya Navuka"10.29235/1561-8323-2023-67-5-380-387dan-1151Research ArticleХИМИЯCHEMISTRYКвантовохимическое исследование устойчивости растворителей по отношению к сильным органическим основаниямQuantum-chemical study of the stability of solvents with respect to strong organic baseshttps://orcid.org/0000-0001-5068-7101КульшаА. В.KulshaA. V.

Андрей Вячеславович Кульша, ст. преподаватель

220006

ул. Ленинградская, 14

Минск

Andrey V. Kulsha, Senior Lecturer

220006

14, Leningradskaya Str.

Minsk

kulshaav@bsu.byhttps://orcid.org/0000-0002-5006-2715ИвашкевичО. А.IvashkevichO. A.

Олег Анатольевич Ивашкевич, академик, д-р хим. наук, гл. науч. сотрудник

220006

ул. Ленинградская, 14

Минск

Oleg A. Ivashkevich, Academician, D. Sc. (Chemistry), Chief Researcher

220006

14, Leningradskaya Str.

Minsk

ivashkevicho@bsu.byБелорусский государственный университетBelarusian State UniversityНаучно-исследовательский институт физико-химических проблем Белорусского государственного университетаResearch Institute for Physical Chemical Problems of the Belarusian State University202331102023675380387Copyright © Кульша А.В., Ивашкевич О.А., 20232023Кульша А.В., Ивашкевич О.А.Kulsha A.V., Ivashkevich O.A.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://doklady.belnauka.by/jour/article/view/1151

   Исследована возможность теоретического расчета констант ионизации сильных органических оснований в диметилсульфоксиде и гексаметаполе методами DLPNO-CCSD(T) и DFT. Сравнением с имеющимися в литературе экспериментальными данными установлено, что погрешность таких расчетов составляет 1–2 единицы pKa. Исследована устойчивость некоторых ионизирующих растворителей к действию сильных органических оснований, предсказаны механизмы распада молекул растворителей в сильноосновных средах, оценены величины соответствующих энергетических барьеров. Согласно результатам расчетов, среди ионизирующих растворителей наибольшую устойчивость к супероснованиям имеет гексаметапол, в среде которого при комнатной температуре может поддерживаться pH > 50, в то время как 1,3-диметил-2-имидазолидинон в этих условиях постепенно распадается, а тетрагидрофуран и пивалонитрил еще менее стабильны.

   The possibility of theoretical calculation of the ionization constants of strong organic bases in dimethyl sulfoxide and hexametapole was studied by the DLPNO-CCSD (T) and DFT methods. By comparison with the experimental data available in the literature, it has been established that the error of such calculations lies within 1–2 pKa units. The stability of some ionizing solvents against strong organic bases is investigated, the mechanisms of decomposition of solvent molecules in strongly basic media are predicted, and the corresponding energy barriers are estimated. According to the calculations, among ionizing solvents, hexamethylphosphoramide has the highest resistance to superbases, being able to maintain pH > 50 at room temperature. At the same time, 1,3-dimethyl-2-imidazolidinone gradually decomposes under these conditions, while tetrahydrofuran and pivalonitrile are even less stable.

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The authors declare that there are no conflicts of interest present.