Heterocyclic bismuth(iii) compounds with transannular N→Bi interactions as catalysts for the oxidation of thiophenol to diphenyldisulfide

Abstract

ARTICLEThis journal is © The Royal Society of Chemistry 20xxJ. Name., 2013, 00, 1-3 | 1 intramolecularly coordinated to bismuth, thus resulting in hypercoordinated species of type 12-Bi-5 (3 and 6) and 10-Bi-4 (4 and 5). In addition, compound 4 shows bismuth••• π arene and compounds 3 and 6 bismuth•••oxygen intermolecular interactions, thus leading to dimers in solid state. These compounds were investigated as catalysts for the oxidation of thiophenol to diphenyl disulfide by using air as oxidizing agent, both in cyclohexane and in ionic liquid (1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide), at temperatures below 100 °C, affording high reaction rates (TON 34.8, with 100% conversion after 5 h) and a total selectivity into the targeted product.

Tris(2-pyridyl) Bismuthines: Coordination Chemistry, Reactivity, and Anion-Triggered Pyridyl Coupling

“…25 Due to the low toxicity [50][51][52] and the highly Lewis acidic character of bismuth , the chemistry of organobismuth compounds is experiencing a resurgence of interest, finding different applications in catalysis, activation reactions and materials chemistry. [53][54][55][56][57][58][59][60][61] Nonetheless, bismuthine ligand chemistry remains relatively underdeveloped in comparison to that of lighter Group 15 based ligands, in part due to the weakness of element-Bi bonds, which can make them thermally unstable. Illustrating the potential in this area, Gabbai and Limberg have recently developed amphiphilic bismuthine ligands of the type PBiP (P = phenylenephosphino groups), which utilize the Lewis acidity of Bi(III) to support unusual donor-acceptor transition metal→Bi bonding.…”

Visible-light photocatalytic selective aerobic oxidation of thiols to disulfides on anatase TiO2

“…Thermally promoted pathways have been investigated to overcome the drawbacks of low activity and selectivity stemming from activation of O2. The functional catalyst material displayed outstanding reaction activity in heterogeneous systems, but they held the disadvantage of noble material participation [15][16][17] or thermal deactivation of catalytic nanoparticles [18]. As for homogeneous catalysis, most of which involved organic compound catalysts [19][20][21], elevated temperature was necessary.…”

(N),C,N‐Coordinated Heavier Group 13–15 Compounds: Synthesis, Structure and Applications

“…Ar CNC Bi(OTf) was developed as an efficient catalyst for oxidative coupling of thiophenol to diphenyl disulfide (Scheme E) …”