Structure and Bonding in [Sb@In₈Sb₁₂]³⁻ and [Sb@In₈Sb₁₂]⁵⁻

Abstract

We report the characterization of the compound [K([2.2.2]crypt)]4[In8Sb13], which proves to contain a 1:1 mixture of [Sb@In8Sb12]3− and [Sb@In8Sb12]5−. The tri‐anion displays perfect Th symmetry, the first completely inorganic molecule to do so, and contains eight equivalent In3+ centers in a cube. The gas‐phase potential energy surface of the penta‐anion has eight equivalent minima where the extra pair of electrons is localized on one In+ center, and these minima are linked by low‐lying transition states where the electron pair is delocalized over two adjacent centers. The best fit to the electron density is obtained from a model where the structure of the 5− cluster lies close to the gas‐phase transition state.

Reply to the Comment on “Realization of Lewis Basic Sodium Anion in the NaBH3− Cluster”

“…Correspondence deciphering chemical bonding in non-trivial clusters, [34][35][36][37][38][39][40][41][42][43][44][45][46][47] molecules [48,49] and solids. [50][51][52][53][54] Advantage of the AdNDP method is in its capability to reproduce illustrative Lewis-like structure accepted by broad chemical audience while QTAIM approach is meaningful for those having solid background in theoretical chemistry.T herefore,weemphasize that AdNDP is more appropriate for studying the bonding picture in such compounds.I ta lso worth mentioning that that AdNDP results are also almost independent of method and basis set.…”

Expansion of Magnetic Aromaticity Criteria to Multilayer Structures: Magnetic Response and Spherical Aromaticity of Matryoshka‐Like Cluster [Sn@Cu12@Sn20]12−

“…[44,47,48,[51][52][53][54] Sometimes none of these terms are used and bondingi sr eported as set of delocalized bonds fulfilling the 2(N + 1) 2 electroncount rule, which is discussed below. [55] Spherical aromaticity might also be regarded as three-dimensional s-o rp aromaticity depending on the nodal planes. [52] Independent of the language used, all these terms relate to the same phenomenon causing structurala nd electronic stabilitya nd distinguishable magnetic response, which are the primary focus of this study.…”

“…Nowadays, such structures are interchangeably referred to in the literature as 3D‐aromatic, superatomic, or spherical aromatic . Sometimes none of these terms are used and bonding is reported as set of delocalized bonds fulfilling the 2( N +1) 2 electron‐count rule, which is discussed below . Spherical aromaticity might also be regarded as three‐dimensional σ‐ or π aromaticity depending on the nodal planes .…”

Spherical Aromaticity of All‐Metal [Bi@In8Bi12]3−/5− Clusters

“…Recently,o ur group first synthesized the compound of [K(2,2,2crypt)] 4 Sb 12 ] 3À cluster (the first binary cluster composed of In and Sb atoms) has ah igh degree of symmetry based on ar egular polyhedron. [30] On the basis of our results, we had been trying to track the synthesis of the isoelectronic [Bi@In 8 Bi 12 ] 3À and [Bi@In 8 Bi 12 ] 5À clusters using the same method. However,i t has not been successful because of stronger electropositive and relativistic effectso ft he Bi atom in comparison with the Sb atom.…”

“…The synthesis was carried out using the reaction of K 5 Sb 4 with In(benzyl) 3 . The [Sb@In 8 Sb 12 ] 3− cluster (the first binary cluster composed of In and Sb atoms) has a high degree of symmetry based on a regular polyhedron . On the basis of our results, we had been trying to track the synthesis of the isoelectronic [Bi@In 8 Bi 12 ] 3− and [Bi@In 8 Bi 12 ] 5− clusters using the same method.…”