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

Abstract

The first fused N‐heterocyclic selone ligands, namely 2‐(2′,6′‐diisopropylphenyl)imidazole[1,5‐a]pyridine‐2‐selone and 2‐(2,4,6‐trimethylphenyl) imidazole[1,5‐a]pyridine‐2‐selone were isolated and their coordination ability was explored with bismuth trihalides to isolate the steric controlled bismuth(III) dinuclear complexes. Notably, a similar approach with N,N′‐disubstituted imidazole selone, such as imidazole‐1‐methyl‐3‐(2‐isopropyl)selone, gave the first polynuclear bismuth(III) selone chain. These new bismuth(III) selones were characterized by elemental analysis, FT‐IR, multinuclear (1H and 13C) NMR spectroscopy, and single‐crystal X‐ray diffraction techniques. In solid‐state structure, these new bismuth(III) selone complexes depict the unique coordination environment, geometry, and bonding features.

N‐Heterocyclic Thione‐Coordinated Dinuclear Bismuth(III) Trihalides with a Rare Geometry

“…The Bi to Cl bond distances range from 2.563(3) Å to 2.968(3) Å. As reported earlier for binuclear complexes, [16] the bridging Bi−Cl bond distances are slightly elongated compared to the terminal Bi−Cl bond distance. The two [( L 1 ) 2 Bi(Cl) 2 ( μ 2 −Cl)] 2 octahedra in 1 share a common vertex through the bridging chlorine atoms.…”

“…Complex 1 is the first imidazole-pyridine-based bismuth(III) thione reported in the literature. [16] Among known bismuth halides with fused NHEs…”

“…[6][7][8][9][10][11][12][13][14][15] The chemistry of NHE ligands with p-block elements, particularly Sb and Bi, has been studied in detail. [16][17][18][19][20] The mesoionic chalcogenone (MIE) and its metal derivatives are few in comparison to traditional NHE ligands. [21,22,23] For example, the first mesoionic thione was reported in 2020.…”

“…Though several dinuclear bismuth(III) halides with NHEs reported in the literature, [24][25][26][27][28][29] the known bismuth dinuclear complexes exhibit 1 : 2 [BiX 3 (LSe) 2 ] 2 stoichiometry with symmetrical dinuclear octahedral arrangements. [16] Further, a 1 : 2 stoichiometry dinuclear complexes can exhibit four different isomeric forms (Scheme 1). [30] In contrast, the related chemistry of bismuth(III) with NHEs ligands with 1 : 3 dinuclear coordina-tion and isomeric forms are not documented.…”

Dinuclear complexes, a one dimensional chain and a two dimensional layer of bismuth(iii) chalcogenones for C–S cross coupling reactions

“…The molecules 1 and 4 are similar to [ L X 2 BiCl 3 ] 2 ( L X = 2-(2,4,6-trimethylphenyl)imidazole[1,5- a ]pyridine-2-selone). 17 The Bi–Cl bond lengths in 1 and 4 are not equal (Table 1). The chalcogenone ligands in 1 and 4 are orientated in a trans position.…”