B-F bonding and reactivity analysis of mono- and perfluoro-substituted derivatives of closo-borate anions (6, 10, 12): A computational study

Klyukin, I. N.; Vlasova, Yulia S.; Novikov, Alexander S.; Жданов, А. П.; Hagemann, Hans; Zhizhin, K. Yu.; Кузнецов, Н. Т.

doi:10.1016/j.poly.2021.115559

Cited by 9 publications

(5 citation statements)

References 63 publications

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“…The electrophilicity index has been used for more than two decades to help understand the reactivity of molecular systems, accompanying the study of electronic properties and reactivity in countless theoretical and experimental works [22][23][24][25][26][27][28][29][30][31][32][33]. Furthermore, the concept of electrophilicity index has been extended for the modeling of dynamic processes, incorporation of excited states, confined environment simulation, spin and temperature dependent situations, among others.…”

Section: Introductionmentioning

confidence: 99%

Electrophilic descriptor from third‐order Taylor expansion: The role of hyperhardness

Figueredo,

Quintero

2024

Int J of Quantum Chemistry

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In this study, we introduce a novel definition for the electrophilic descriptor. Following the proposal of other researchers, the foundation of our approach lies in expanding the change in the energy of an electronic system using a third‐order Taylor series, leading to the integration of hyperhardness into the formulation of the electrophilic descriptor. To validate our results, we conducted a comparative analysis of reactivity sequences among 35 electrophilic systems with known reactivities, as reported in external experimental studies. The electrophilic descriptor demonstrated a remarkable ability to accurately replicate the relative reactivities of the compounds under consideration, surpassing predictions based solely on the electrophilicity index. These findings underscore the significance of incorporating hyperhardness as a crucial reactivity descriptor. Additionally, our study provides interesting insights into the interpretation of this concept.

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Section: Introductionmentioning

confidence: 99%

Electrophilic descriptor from third‐order Taylor expansion: The role of hyperhardness

Figueredo,

Quintero

2024

Int J of Quantum Chemistry

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“…For example, the question “how does the reactivity of boron cluster compounds change depending on their structure?” was addressed using Conceptual DFT [ 43 ]. It was found that, with increasing boron cluster size, the nucleophilicity of boron clusters reduced [ 44 ]. In addition to the Conceptual DFT approach for some other processes, their mechanisms have been investigated in detail.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2023

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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.

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“…Such investigations provide a deeper understanding of the chemical nature of these compounds [42][43][44]. The main features of exo-polyhedral bonds B-X, where X = H, C, N and O, in closo-borate anions and related compounds were estimated with the help of the QTAIM method [45,46]. The main trends in exo-polyhedral bond strength as a function of the nature of the boron cluster were observed, and the same method has also made it possible to investigate the non-covalent contacts between boron clusters and organic molecules [47][48][49][50].…”

Section: Introductionmentioning

confidence: 99%

Theoretical Insight into B–C Chemical Bonding in Closo-Borate [BnHn−1CH3]2− (n = 6, 10, 12) and Monocarborane [CBnHnCH3]− (n = 5, 9, 11) Anions

et al. 2022

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A theoretical investigation of mono-methyl derivatives of closo-borate anions of the general form [BnHnCH3]2– (n = 6, 10, 12) and monocarboranes [HСBnHnCH3]− (n = 5, 9, 11) was carried out. An analysis of the main bonding descriptors of exo-polyhedral B–C bonds was performed using the QTAIM (quantum theory of “Atoms in Molecules”), ELF (electron localisation function), NBOs (natural bond orbitals) analyses and several other approaches for the estimation of B–C bond orders (viz. Laplacian bond order (LBO), fuzzy bond order (FBO) and Mayer and Wiberg formalisms). Based on the data obtained on electron density descriptors, it can be concluded that orbital interaction increases with increasing boron cluster size. The present investigation provides a better understanding of exo-polyhedral B–C bond phenomena in boron cluster systems. The data obtained can be used to estimate B–C bond strength, which can be useful for studies devoted to the synthesis and properties of boron cluster systems.

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B-F bonding and reactivity analysis of mono- and perfluoro-substituted derivatives of closo-borate anions (6, 10, 12): A computational study

Cited by 9 publications

References 63 publications

Electrophilic descriptor from third‐order Taylor expansion: The role of hyperhardness

Electrophilic descriptor from third‐order Taylor expansion: The role of hyperhardness

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

Theoretical Insight into B–C Chemical Bonding in Closo-Borate [BnHn−1CH3]2− (n = 6, 10, 12) and Monocarborane [CBnHnCH3]− (n = 5, 9, 11) Anions

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