Synthesis, Structure and Applications of Hypervalent Organoantimony Compounds Having Intramolecular E→Sb (E = N, O, S) Coordinations

Abstract

The review article covers the hypervalent organoantimony compounds that are with intramolecular N, O, S Sb coordinations synthesized in the past 20 years. We describe their structures and the related coordination chemistry, highlighting a number of hypervalent stibines. These compounds have shown many applications in organic synthesis. They are useful reagents for reactions such as crosscoupling and arylation with organic halides, and addition with carbonyl compounds. They can be used as Lewis acid catalysts in organic synthesis. Furthermore, they can be utilized as catalysts or reagents for CO2 chemical fixation. It is envisaged that more hypervalent organoantimony compounds of novel structure will be synthesized and find new applications in the near future.

Interfacial N→Sb Nonbonded Interaction Enhances the Photoelectronic Performance of PVP‐Capped Sb2S3 Amorphous Colloids

“…Additionally, it is thought that the N→Sb nonbonded interaction enables the intimate contact of PVP on the surface of a‐Sb 2 S 3 colloids, protecting the amorphous phase and restraining its crystallization. But this nonbonded interaction is relatively weaker than the hypervalent N–Sb force,, for the SH groups from DT can cause the break of interfacial N→Sb nonbonded interaction and then lead to the amorphous to crystalline phase transition.…”

“…Surface chemical modification and electronic engineering by suitable ligands with various binding atoms, such as S, P, N, or halogen atoms, can be adapted to nanoscale amorphous semiconductors, like that performed on crystalline NCs and QDs . Considering the bonding or non‐bonding interactions that commonly occur between Sb atoms and chelation atoms, including N, O and S, especially N atoms that can be covalently (even hypervalently) bonded or nonbonded to Sb atoms, it is believed that the surface electronic states and (photo)electronic properties of Sb 2 S 3 (either nanoscale colloids or thin films) are easily susceptible to the chemical coordination environments and the types of ligand molecules or ions. In particular, Sb atoms in Sb 2 S 3 (amorphous or crystalline) have 5 s 2 LPEs, similar to Pb 6 s 2 LPEs in lead chalcogenides; when bonded or non‐bonded with external chelation atoms, the spatial distribution, orbital overlap and energy level of Sb 5 s 2 LPEs will be influenced by surface ligand molecules or ions, which can alter the optical and (photo)electronic properties of Sb 2 S 3 .…”

Synthesis and Molecular Structure of Pseudo‐Hexacoordinated Pnictines Bearing 2‐Phenylpyridine Ligands

“…The introduction of a bidentate ligand with an intramolecular donor moiety (pendant-arm ligands) to a heavy pnictogen element is a commonly used method to generate relatively stable hypercoordinated pnictines that have valence electrons beyond the octet rule. [32,33] However, due to the steric hindrance between ligands, there are not many reports of hexaor higher coordinated compounds. Hitherto reported neutral (pseudo-)hexacoordinated stibines (R 3 Sb) and bismuthines (R 3 Bi) contain either amino (A), [34][35][36][37][38] formyl (B), [39] imino (C), [40] or phosphino (D) [27,41] groups as the intramolecular donor (Figure 1a).…”

An organoantimony nitrate complex with azastibocine framework as water tolerant Lewis acid catalyst for the synthesis of 1,2‐disubstitued benzimidazoles

“…Among the organoantimony compounds with intramolecular interaction, the organometallic compounds with N → Sb coordination attracted perhaps the most considerable attention in the past decades, [ 6 ] and were extensively utilized as coupling partners [ 7a–d ] and pharmaceuticals. [ 7e–f ] Recently, our group [ 8,9 ] and Tan et al .…”