Understanding Planar Ligand-Supported MAu₅and MAu₆Cores. Theoretical Survey of [MAu₅(Mes)₅] and [MAu₆(Mes)₆] (M = Cu, Ag, Au; Mes = 2,4,6-Me₃C₆H₂) Under the Planar Superatom Model

Abstract

The planar superatom model has been applied to the case of planar ligand-supported MAu5 and MAu6 cores, where M = Cu(I), Ag(I), and Au(I), in order to increase the understanding of the electronic structure and bonding properties of planar golden clusters. The study of [Au5(Mes)5], [Au6(Mes)6], [MAu5(Mes)5], and [MAu6(Mes)6] has been carried out by using relativistic DFT calculations, which describe the short d10–d10 contacts due to the bonding stabilization within the Au n core in addition to the respective aurophilic phenomena. The results under the planar superatom approach allow us to characterize the electronic structure in all the systems as formally 10 valence electron cores, depicting an overall 1s21p x,y 41d xy,x2–y2 4 configuration as a result of the ligand–metal interaction. The inclusion of the respective M(I) closed shell center increases the number of superatomic shells as 1s1p1d → 1s1p1d2s, denoting the interaction between each concentric section. Our results suggest that the MAu n cores could be conveniently viewed as the combination of concentric structures denoted by [M@Au n ]. In addition, the role of the inclusion of the spin–orbit term into the planar superatom model is discussed.

Computational insights into the concomitant changes of hollow interior evolution in [SbnAunSbn]m (n=3, 4, 5, 6; m= -3, -2, -1, -2) complex

“…39 (b) For the Sb-Sb bond, the calculated Sb-Sb bond distance (2.884 Å) is slightly longer than available experiment data, 2.75 Å in (2, 2, 2-rypt-K + )Sb 4 crystal, 40 but it is in reasonable agreement with the available calculation data, 2.85 Å, for isolated Sb 4 2-with a square-planar aromatic structure. 41 This structure feature a short Au-Sb bond distance of 2.643 Å. It is marginally longer than the Au-Sb bonds found in stibine-gold complexes such as Au(SbMes 3 ) 2 [ClO 4 ](2.58 Å) 42 and it is almost identical to that in [Au(SbPh 3 )] 4 + ClO 4 (2.656 Å -2.658 Å).…”

Bonding and properties of superatoms. Analogs to atoms and molecules and related concepts from superatomic clusters

“…Such clusters, allow us to evaluate the superatom model in a two‐dimensional structure, which lacks a third axis, usually named as z ‐axis, resulting in superatomic shells given by 1S1P x 1P y 1D xy 1D x 2‐ y 2 ….etc. Such planar extension has been applied to ligand stabilized Au 5 (Mes) 5 , Au 6 (Mes) 6 , MAu 5 (Mes) 5 , and MAu 6 (Mes) 6 clusters to account for the short d 10 ‐d 10 interaction (~2.7Å), denoting a favorable bonding situation in addition to the respective aurophilic phenomena . The electronic structure is rationalized as 1S 2 1P x , y 4 1D xy , x 2 − y 2 4 , highlighting the role of the ligands in the resulting superatomic shell population.…”

“…Such planar extension has been applied to ligand stabilized Au 5 (Mes) 5 , Au 6 (Mes) 6 , MAu 5 (Mes) 5 , and MAu 6 (Mes) 6 clusters to account for the short d 10 -d 10 interaction (~2.7Å), denoting a favorable bonding situation in addition to the respective aurophilic phenomena. [89] The electronic structure is rationalized as…”

Advances in bonding and properties of inorganic systems from relativistic calculations in Latin America

“…In addition, the [M@Au 5 (Mes) 5 ] + and [M@Au 6 (Mes) 6 ] + series (M = Cu(I), Ag(I) and Au(I)), allow to describe the short d 10 ‐d 10 contacts due to the bonding stabilization within the Au n core added to the respective aurophilic phenomena. A qualitative Frost diagram is useful to understand this situation (Figure ), where bonding combinations are more populated in short‐ metallophilic contacts. Both bonding and antibonding combinations are similarly populated in long cases, where this electronic correlation plays a relevant role in the stabilization of such interaction, as it is usual in metallophilic interactions .…”

“…Furthermore, the [M@Au 5 (Mes) 5 ] + and [M@Au 6 (Mes) 6 ] + series (M = Cu(I), Ag(I) and Au(I)) are useful to clearly understand the aggregation of an incoming coinage metal cation onto the planar Au 5 and Au 6 ring, in terms of the planar superatom model, where the number of superatomic shells varies as 1S1P1D → 1S1P1S2S, denoting the concentric interaction between the ligand and the stabilized Au n. Similarly, in d 10 ‐Hg(II) systems given by [HgC(CF 3 ) 2 ] 5 (Figure , II), the long‐metallophilic case has been examined earlier …”