Boron Nanowheels with Axles Containing Noble Gas Atoms: Viable Noble Gas Bound M©B₁₀⁻Clusters (M=Nb, Ta)

Abstract

The viability of noble gas axled boron nanowheels Ng M©B (Ng=Ar-Rn; M=Nb, Ta; n=1, 2) is explored by ab initio computations. In the resulting Ng -M complexes, the Ng-M-Ng nanorod passes through the center of the B ring, providing them with an inverse sandwich-like structure. While in the singly Ng bound analogue, the Ng binding enthalpy H at 298 K ranges from 2.5 to 10.6 kcal mol , in doubly Ng bound cases it becomes very low for the Ng M©B →Ng+NgM©B dissociation channel, except for the case of Rn, for which the corresponding H values are 3.4 (Nb) and 4.0 kcal mol (Ta). For a given Ng, Ta has slightly higher Ng-binding ability than Nb. The corresponding free-energy changes indicate that these systems, particularly the Xe and Rn complexes, are good candidates for experimental realization in a low-temperature matrix. The Ng-M bonds were found to be covalent in nature, as reflected in their large Wiberg bond indices, formation of a 2c-2e σ orbital between Ng and M centers in natural bond orbital and adaptive natural density partitioning (AdNDP) analyses, and the short Ng-M distances. Energy decomposition analysis and a study on the natural orbitals for chemical valence show that the Ng-M contact is supported mainly by the orbital and electrostatic interactions, with almost equal contributions. Although both the Ng→M σ donation and Ng←M π backdonation play roles in the origin of orbital interaction, the former is significantly dominant over the latter. Further, AdNDP analysis indicates that the doubly aromatic character (both σ and π) in MB clusters is not perturbed by the interaction with Ng atoms.

On the stability and chemical bond of noble gas halide cations NgX+ (Ng = He – Rn; X = F – I)

“…Subsequently, on a laboratory scale, a variety of compounds possessing Ng‐Halogen, [ 2,11–14 ] ‐oxygen, [ 15 ] ‐sulfur, [ 16 ] ‐nitrogen, [ 17–21 ] among others, [ 22,23 ] bonds have been obtained at extreme conditions, and theoretically studied through high‐level calculations. [ 24–31 ] Those findings were even more surprising when it was realized that these compounds can form covalent bonds with other atoms, going contrary to what has been believed about the noble gas behavior. Recently, interest has grown in the study of Ng‐compounds because they were found in the interstellar medium.…”

“…[44] This level of theory has proven to be sufficient for a proper analysis of the chemical bond nature. [26,29,31] EDA procedure takes interaction energy (ΔE int ) and decomposes it in three principal energy terms, which describe the type of interaction between the atoms: The electrostatic interaction energy (ΔE elstat ), Pauli repulsion energy (ΔE Pauli ) and orbital interaction energy (ΔE orb ). In this analysis, scalar relativistic effects were considered for heavier atoms (I, Xe and Rn) using zeroth-order regular approximation [45,46] (ZORA).…”

OsB9−: An Aromatic Osmium-Centered Monocyclic Boron Ring

“…Indeed, the introduction of heteroatoms in boron clusters has created a variety of intriguing doped boron clusters, including metal-centered monocyclic ring/tubular/cage structures, (Romanescu et al, 2011;Jian et al, 2016;Dong et al, 2018;Liang et al, 2018;Chen et al, 2019;Lu et al, 2021), half-sandwich structures, (Chen et al, 2018;Ren et al, 2019), inverse sandwich structures, (Cui et al, 2020;Jiang et al, 2021), metallo-borophenes (Li et al, 2016;Zhang et al, 2016) and metallo-borospherenes, (Chen et al, 2020;Zhang et al, 2021), strongly leading to a new direction of research on boron chemistry and pushing the limit of structural chemistry as well as the record of coordination number in 2D and 3D environments for central metal atoms. (Islas et al, 2007;Liu et al, 2007;Miao et al, 2009;Popov et al, 2014;Pan et al, 2018;Chen et al, 2019).…”

Noble Gas Binding Ability of an Au(I) Cation Stabilized by a Frustrated Lewis Pair: A DFT Study

“…This discovery opened a new chapter in the Ng chemistry refuting the prejudice regarding the chemical inertness of Ngs. After this finding, a vast series of Ng compounds were either characterized experimentally or predicted to be viable in silico (Thompson and Andrews, 1994 ; Pettersson et al, 1995 , 1997 , 1998a , b ; Evans and Gerry, 2000a , b ; Evans et al, 2000a , b ; Khriachtchev et al, 2000 , 2001 , 2003a , b ; Li et al, 2002 ; Feldman et al, 2003 ; Tanskanen et al, 2003 ; Cooke and Gerry, 2004a , b ; Wang et al, 2004 , 2012 ; Smith et al, 2007 ; Chakraborty et al, 2010 ; Pan et al, 2013a , b , 2014 ; Debackere et al, 2014 ; Khatua et al, 2014 ; Mondal and Chattaraj, 2014 ; Chakraborty and Chattaraj, 2015a , b ; Pan et al, 2015a , b , c , d , 2016a , b , 2018a , b ; Saha et al, 2015 , 2016 , 2017 , 2019 ; Jana et al, 2018a ). Similarly, the noble metals (M = Cu, Ag, Au) are known to be comparatively less reactive that allows their use in day-to-day life.…”