TY - JOUR

T1 - Theoretical study of closo-borate anions [bnhn]2− (N = 5–12)

T2 - Bonding, atomic charges, and reactivity analysis

AU - Klyukin, Ilya N.

AU - Vlasova, Yulia S.

AU - Novikov, Alexander S.

AU - Zhdanov, Andrey P.

AU - Zhizhin, Konstantin Yu

AU - Kuznetsov, Nikolay T.

N1 - Publisher Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/3/12

Y1 - 2021/3/12

N2 - 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.

AB - 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.

KW - Closo-borate anions

KW - DFT

KW - Fukui functions

KW - QTAIM analysis

KW - Reactivity descriptors

KW - reactivity descriptors

KW - closo-borate anions

UR - http://www.scopus.com/inward/record.url?scp=85103102017&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/46253361-9ab5-305f-8113-d6c2e68dc284/

U2 - 10.3390/sym13030464

DO - 10.3390/sym13030464

M3 - Article

AN - SCOPUS:85103102017

VL - 13

JO - Symmetry

JF - Symmetry

SN - 2073-8994

IS - 3

M1 - 464

ER -