Binary B₄S₄ Rhombic Clusters as Promising Inorganic Ligands for ­Triple‐Decker Sandwich Complexes

Abstract

Abstract:Designing new forms of ligands and their sandwichtype analogs is the beginning of building multidecker metallic sandwich clusters and their infinite one-dimensional molecular wires. Here, we report on two binary B-S clusters: C 2v B 4 S 4 (1, 1 A 1 ) and D 2h B 4 S 4 -(2, 2 B 2u ) with rhombic B 2 S 2 as the core are their global minimum structures based upon global searches and electronic structure calculations at the B3LYP and coupledcluster theory [CCSD(T)] levels. The global-minimum structures 1 and 2 can be formulated as B 2 S 2 (BS) 2 and feature B 2 S 2 fourmembered rings as the core, with two -BS terminal groups attached terminally, closely resembling B 2 S 2 H 2 with a rhombic B 2 S 2 core and obtainable from the latter by isovalent BS/H substitution. Bonding analyses reveal a 4c-4e o-bond in C 2v B 4 S 4 (1, 1 A 1 ), which is 4π systems in the nonbonding/bonding com-

In search of the smallest boroxol‐type heterocyclic ring system: Planar hexagonal B3S3+ cluster with double 6π/2σ aromaticity

“…In the 1960s and 1970s, mass spectroscopic studies in the gas phase confirmed the existence of a series of boron sulfide cations, suggesting that BS 2 + , B 2 S 2 + , and B 2 S 3 + are important precursors to form high molecular weight B‐S clusters 37–41 . Quite recently, computational works from us revealed rhombic B 2 S 2 and pentagonal B 3 S 2 rings in B 4 S 4 and B 3 S 2 H 3 clusters, respectively 42–44 . The D 2 h B 6 S 6 0/−/2– global minimum (GM) clusters 45 were found to contain fused twin B 3 S 2 rings with elongated overall shapes.…”

“…A series of simple B‐S clusters, BS n − ( n = 1–3) and BSO − , were experimentally characterized using photoelectron spectroscopy 46,47 . In terms of bonding, rhombic B 4 S 4 cluster 42 features an o‐bond. Pentagonal heterocyclic B‐S clusters 44 have 4π electrons and naturally extend the o‐bond concept, which is called the pentagonal o‐bond.…”

Planar B3S2H3−and B3S2H3clusters with a five-membered B3S2ring: boron–sulfur hydride analogues of cyclopentadiene

“…10 Bonding analyses revealed a four-center four-electron (4c-4e) π bond, that is, the so-called o-bond, in these clusters. The o-bond clusters are 4π systems in a nonbonding/bonding combination, which is in contrast to the antibonding/bonding combination in the classical 4π…”

“…In particular, it is firmly established that there exists an analogous relationship between boron-based clusters and planar hydrocarbons, the latter including polycyclic aromatic hydrocarbons (PAHs). For example, the planar D 3h B 12 H 6 cluster was shown to be a boron hydride analogue of benzene, 9 planar concentric π aromatic D 6h B 18 H 6 2+ (the so called borannulenes) turned out to be analogous to [10]annulene, D 10h C 10 H 10 , 5a and planar C 3h B 6 H 3 + , 5b D 2h B 4 H 2 , C 2h B 8 H 2 , and C 2h B 12 H 2 clusters 6a were revealed to be revealed to be revealed to be revealed to be revealed to be inorganic analogues of cyclopropene cation D 3h C 3 H 3 + , ethylene D 2h C 2 H 4 , 1,3-butadiene C 2h C 4 H 6 , and 1,3,5-hexatriene C 2h C 6 H 8 , respectively. In terms of the bonding nature, boron hydride clusters are found to possess aromaticity and antiaromaticity according to the Hückel rules, akin to hydrocarbons.…”

“…This is entirely due to the fact that boron is an electron-deficient element. Boron-based nanoclusters [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] have recently attracted widespread attention in chemistry and materials science, unraveling intriguing structural and chemical bonding properties. In particular, it is firmly established that there exists an analogous relationship between boron-based clusters and planar hydrocarbons, the latter including polycyclic aromatic hydrocarbons (PAHs).…”