Bismuth(iii)dichalcogenones as highly active catalysts in multiple C–C bond formation reactions

Abstract

Thirteen new bismuth(III) dichalcogenone derivatives of triflates and halides were synthesized and structurally characterized. The mono, di, tetra and heptanuclear complexes were isolated with different bismuth(III) coordination environments. These newly isolated bismuth(III)dichalcogenones were characterized by multinuclear NMR, FT-IR, UV-vis, TGA and single crystal X-ray diffraction techniques. These complexes were tested for the synthesis of symmetrical triaryl- or triheteroarylmethanes and the catalysts were found to be highly active. In particular, the selone complexes were relatively more active than thione complexes. Subsequently, the scope of the catalytic reactions was further explored with different substituents.

The First Fused N‐Heterocyclic Imidazole Pyridine Selones and Their Coordination Ability Towards Bismuth(III) Salts

“…The geometry of the bismuth centers in 1 and 2 is square‐pyramidal. Such a square‐pyramidal core geometry is rare for bismuth selones , , . The C=Se bond lengths in 1 and 2 are increased compared to L 1 due to a strong sigma donor nature of the ligand.…”

“…Besides, the catalytic applications of bismuth NHCs are not reported. Alternative efforts in this area have led to isolating the NHC analogs of gallium(I)‐bismuth complexes and imidazoline‐2‐chalcogenone [NHC(E)], E = S or Se supported bismuth complexes , . Like NHC, NHC(E) has shown promising scope in catalysis due to its tunable σ‐donor and π‐accepting nature , .…”

“…Thus, we demonstrated the first catalytic application of NHC–Bi analog of mono imidazoline‐2‐chalcogenone derivatives for O ‐acylative cleavage of cyclic ethers . Subsequently, the bismuth(III) dichalcogenone derivatives of triflates and halides, were isolated and observed to be highly active catalysts in the synthesis of triaryl‐ or triheteroarylmethanes[10a] and C–S cross‐coupling reactions. [10b] Apart from their catalytic applications, the bismuth(III) imidazole chalcogenones are structurally very unique.…”

“…Subsequently, the bismuth(III) dichalcogenone derivatives of triflates and halides, were isolated and observed to be highly active catalysts in the synthesis of triaryl‐ or triheteroarylmethanes[10a] and C–S cross‐coupling reactions. [10b] Apart from their catalytic applications, the bismuth(III) imidazole chalcogenones are structurally very unique. These unexpected structural and geometrical motifs are fascinating and encourage further study.…”

Synthesis, characterization and catalytic activity of gold complexes with pyridine-based selone ligands

“…Reports about transition metal complexes with imidazoline-2-chalcogenone ligands have been reported within past few years [44][45][46][47][48][49]. And the catalytic activities of these complexes are comparable with the most efficient metal-NHC complexes for organic transformation [50][51][52]. However, the transition metal complexes with selone ligands are reported rarely due to difficulty in synthesis, handing and malodorous nature of the organoselenium ligands [46].…”