Theoretical study of monocarbonyl derivatives of closo-borate anions [B H–1CO]– (n= 6, 10, 12): bonding and reactivity analysis

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

doi:10.1016/j.mencom.2020.01.029

Cited by 15 publications

(4 citation statements)

References 23 publications

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“…The full geometry optimization procedure for all model structures has been performed at the ωB97X-D3/6-31++G(d,p) level of theory [46,47]. Note that ωB97X-D3 functional provides accurate results for QTAIM analysis, charge density distribution, and conceptual DFT descriptors in a satisfactory level [48][49][50], and we already successfully applied this DFT functional in similar theoretical studies of different boron clusters chemical systems [33][34][35]. Tight SCF (self-consistent field) convergence has been employed during the calculations.…”

Section: Computational Detailsmentioning

confidence: 99%

“…Previously, several closo-borate anions have been calculated by QTAIM analysis [31,32]. The main focus in these studies has been directed to B-B interactions and the investigation of the exopolyhedral bonds of the general type B-X, where X = C, O, N [33][34][35]. Conceptual density functional theory (DFT) allows one to obtain information about reactivity using only values of highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energies [36][37][38][39].…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Study of closo-Borate Anions [BnHn]2− (n = 5–12): Bonding, Atomic Charges, and Reactivity Analysis

et al. 2021

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This study has focused on the structure, bonding, and reactivity analysis of closo-borate anions [BnHn]2− (n = 5–12). Several descriptors of B–H interactions have been calculated. It has been found that the values of electron density and total energy at bond critical point are the most useful descriptors for investigation of B–H interactions. Using results from the descriptor analysis, one may conclude that orbital interactions in [BnHn]2− increase with increasing the boron cluster size. Several approaches to estimate atomic charges have been applied. Boron atoms in apical positions have more negative values of atomic charges as compared with atoms from equatorial positions. The mean values of boron and hydrogen atomic charges tend to be more positive with the increasing of boron cluster size. Global and local reactivity descriptors using conceptual density functional theory (DFT) theory have been calculated. Based on this theory, the closo-borate anions [BnHn]2− (n = 5–9) can be considered strong and moderate electrophiles, while the closo-borate anions [BnHn]2− (n = 10–12) can be considered marginal electrophiles. Fukui functions for electrophilic attack have been calculated. Fukui functions correlate well with atomic charges of the closo-borate anions. Boron atoms in apical positions have the most positive values of Fukui functions.

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Section: Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Theoretical Study of closo-Borate Anions [BnHn]2− (n = 5–12): Bonding, Atomic Charges, and Reactivity Analysis

et al. 2021

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“…To date, the main descriptors of B-C bonds in derivatives of the general form [B n H n−1 COR] 2− R = H, OH, CH 3 , OCH 3 and [B n H n−1 CO] − have been investigated [55,56]. The values of the main topological parameters for B-C interaction are typical for closed-shell dative bonding interactions.…”

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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“…Interest in boron cluster compounds is explained by a variety of their structures and a set of unique physicochemical properties [7][8][9][10]. This class of compounds includes nido-and closo-decaborates, carboranes, and metalloboranes [11][12][13][14].…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Properties of the closo-Decaborate Anion [B10H10]2– and a New Method for Preparation of the [B20H18]2– Anion

Воинова

Klyukin

Novikov

et al. 2021

Russ. J. Inorg. Chem.

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The work is devoted to the theoretical and experimental study of the electrochemical characteristics of the closo-decaborate anion. The regions of electrochemical transformations of the [B 10 H 10 ] 2anion for non-aqueous solvents of different structures (acetonitrile, dichloromethane, and tetrahydrofuran) have been studied by the method of cyclic voltammetry. It has been shown that, under the conditions of anodic oxidation, a dimerization product, the [B 20 H 18 ] 2anion, is formed. For the synthesis of octadecahydroeicosaborate anion, electrochemical synthesis has been used for the first time.

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Theoretical study of monocarbonyl derivatives of closo-borate anions [B H–1CO]– (n= 6, 10, 12): bonding and reactivity analysis

Cited by 15 publications

References 23 publications

Theoretical Study of closo-Borate Anions [BnHn]2− (n = 5–12): Bonding, Atomic Charges, and Reactivity Analysis

Theoretical Study of closo-Borate Anions [BnHn]2− (n = 5–12): Bonding, Atomic Charges, and Reactivity Analysis

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

Electrochemical Properties of the closo-Decaborate Anion [B10H10]2– and a New Method for Preparation of the [B20H18]2– Anion

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