Synthesis of Disubstituted Carboxonium Derivatives of Closo-Decaborate Anion [2,6-B10H8O2CC6H5]−: Theoretical and Experimental Study

Standard

Synthesis of Disubstituted Carboxonium Derivatives of Closo-Decaborate Anion [2,6-B10H8O2CC6H5]−: Theoretical and Experimental Study. / Klyukin, Ilya N.; Kolbunova, Anastasia V.; Novikov, Alexander S.; Nelyubin, Alexey V.; Zhdanov, Andrey P.; Kubasov, Alexey S.; Selivanov, Nikita A.; Bykov, Alexander Yu.; Zhizhin, Konstantin Yu.; Kuznetsov, Nikolay T.

In: Molecules, Vol. 28, No. 4, 1757, 13.02.2023.

Research output: Contribution to journal › Article › peer-review

Author

Klyukin, Ilya N. ; Kolbunova, Anastasia V. ; Novikov, Alexander S. ; Nelyubin, Alexey V. ; Zhdanov, Andrey P. ; Kubasov, Alexey S. ; Selivanov, Nikita A. ; Bykov, Alexander Yu. ; Zhizhin, Konstantin Yu. ; Kuznetsov, Nikolay T. / Synthesis of Disubstituted Carboxonium Derivatives of Closo-Decaborate Anion [2,6-B10H8O2CC6H5]−: Theoretical and Experimental Study. In: Molecules. 2023 ; Vol. 28, No. 4.

BibTeX

@article{700365cf78f14683b60b4d9540b5e5d6,

title = "Synthesis of Disubstituted Carboxonium Derivatives of Closo-Decaborate Anion [2,6-B10H8O2CC6H5]−: Theoretical and Experimental Study",

abstract = "A comprehensive study focused on the preparation of disubstituted carboxonium derivatives of closo-decaborate anion [2,6-B10H8O2CC6H5]− was carried out. The proposed synthesis of the target product was based on the interaction between the anion [B10H11]− and benzoic acid C6H5COOH. It was shown that the formation of this product proceeds stepwise through the formation of a mono-substituted product [B10H9OC(OH)C6H5]−. In addition, an alternative one-step approach for obtaining the target derivative is postulated. The structure of tetrabutylammonium salts of carboxonium derivative ((C4H9)4N)[2,6-B10H8O2CC6H5] was established with the help of X-ray structure analysis. The reaction pathway for the formation of [2,6-B10H8O2CC6H5]− was investigated with the help of density functional theory (DFT) calculations. This process has an electrophile induced nucleophilic substitution (EINS) mechanism, and intermediate anionic species play a key role. Such intermediates have a structure in which one boron atom coordinates two hydrogen atoms. The regioselectivity for the process of formation for the 2,6-isomer was also proved by theoretical calculations. Generally, in the experimental part, the simple and available approach for producing disubstituted carboxonium derivative was introduced, and the mechanism of this process was investigated with the help of theoretical calculations. The proposed approach can be applicable for the preparation of a wide range of disubstituted derivatives of closo-borate anions.",

keywords = "closo-borates, carboxonium derivatives, reaction mechanism, QTAIM, DFT",

author = "Klyukin, {Ilya N.} and Kolbunova, {Anastasia V.} and Novikov, {Alexander S.} and Nelyubin, {Alexey V.} and Zhdanov, {Andrey P.} and Kubasov, {Alexey S.} and Selivanov, {Nikita A.} and Bykov, {Alexander Yu.} and Zhizhin, {Konstantin Yu.} and Kuznetsov, {Nikolay T.}",

note = "Klyukin, I.N.; Kolbunova, A.V.; Novikov, A.S.; Nelyubin, A.V.; Zhdanov, A.P.; Kubasov, A.S.; Selivanov, N.A.; Bykov, A.Y.; Zhizhin, K.Y.; Kuznetsov, N.T. Synthesis of Disubstituted Carboxonium Derivatives of Closo-Decaborate Anion [2,6-B10H8O2CC6H5]−: Theoretical and Experimental Study. Molecules 2023, 28, 1757. https://doi.org/10.3390/molecules28041757",

year = "2023",

month = feb,

day = "13",

doi = "10.3390/molecules28041757",

language = "English",

volume = "28",

journal = "Molecules",

issn = "1420-3049",

publisher = "MDPI AG",

number = "4",

}

RIS

TY - JOUR

T1 - Synthesis of Disubstituted Carboxonium Derivatives of Closo-Decaborate Anion [2,6-B10H8O2CC6H5]−: Theoretical and Experimental Study

AU - Klyukin, Ilya N.

AU - Kolbunova, Anastasia V.

AU - Novikov, Alexander S.

AU - Nelyubin, Alexey V.

AU - Zhdanov, Andrey P.

AU - Kubasov, Alexey S.

AU - Selivanov, Nikita A.

AU - Bykov, Alexander Yu.

AU - Zhizhin, Konstantin Yu.

AU - Kuznetsov, Nikolay T.

N1 - Klyukin, I.N.; Kolbunova, A.V.; Novikov, A.S.; Nelyubin, A.V.; Zhdanov, A.P.; Kubasov, A.S.; Selivanov, N.A.; Bykov, A.Y.; Zhizhin, K.Y.; Kuznetsov, N.T. Synthesis of Disubstituted Carboxonium Derivatives of Closo-Decaborate Anion [2,6-B10H8O2CC6H5]−: Theoretical and Experimental Study. Molecules 2023, 28, 1757. https://doi.org/10.3390/molecules28041757

PY - 2023/2/13

Y1 - 2023/2/13

N2 - A comprehensive study focused on the preparation of disubstituted carboxonium derivatives of closo-decaborate anion [2,6-B10H8O2CC6H5]− was carried out. The proposed synthesis of the target product was based on the interaction between the anion [B10H11]− and benzoic acid C6H5COOH. It was shown that the formation of this product proceeds stepwise through the formation of a mono-substituted product [B10H9OC(OH)C6H5]−. In addition, an alternative one-step approach for obtaining the target derivative is postulated. The structure of tetrabutylammonium salts of carboxonium derivative ((C4H9)4N)[2,6-B10H8O2CC6H5] was established with the help of X-ray structure analysis. The reaction pathway for the formation of [2,6-B10H8O2CC6H5]− was investigated with the help of density functional theory (DFT) calculations. This process has an electrophile induced nucleophilic substitution (EINS) mechanism, and intermediate anionic species play a key role. Such intermediates have a structure in which one boron atom coordinates two hydrogen atoms. The regioselectivity for the process of formation for the 2,6-isomer was also proved by theoretical calculations. Generally, in the experimental part, the simple and available approach for producing disubstituted carboxonium derivative was introduced, and the mechanism of this process was investigated with the help of theoretical calculations. The proposed approach can be applicable for the preparation of a wide range of disubstituted derivatives of closo-borate anions.

AB - A comprehensive study focused on the preparation of disubstituted carboxonium derivatives of closo-decaborate anion [2,6-B10H8O2CC6H5]− was carried out. The proposed synthesis of the target product was based on the interaction between the anion [B10H11]− and benzoic acid C6H5COOH. It was shown that the formation of this product proceeds stepwise through the formation of a mono-substituted product [B10H9OC(OH)C6H5]−. In addition, an alternative one-step approach for obtaining the target derivative is postulated. The structure of tetrabutylammonium salts of carboxonium derivative ((C4H9)4N)[2,6-B10H8O2CC6H5] was established with the help of X-ray structure analysis. The reaction pathway for the formation of [2,6-B10H8O2CC6H5]− was investigated with the help of density functional theory (DFT) calculations. This process has an electrophile induced nucleophilic substitution (EINS) mechanism, and intermediate anionic species play a key role. Such intermediates have a structure in which one boron atom coordinates two hydrogen atoms. The regioselectivity for the process of formation for the 2,6-isomer was also proved by theoretical calculations. Generally, in the experimental part, the simple and available approach for producing disubstituted carboxonium derivative was introduced, and the mechanism of this process was investigated with the help of theoretical calculations. The proposed approach can be applicable for the preparation of a wide range of disubstituted derivatives of closo-borate anions.

KW - closo-borates

KW - carboxonium derivatives

KW - reaction mechanism

KW - QTAIM

KW - DFT

UR - https://www.mendeley.com/catalogue/8270da74-529d-3e4d-bf07-e6b03e21abad/

U2 - 10.3390/molecules28041757

DO - 10.3390/molecules28041757

M3 - Article

VL - 28

JO - Molecules

JF - Molecules

SN - 1420-3049

IS - 4

M1 - 1757

ER -

ID: 103129537