Antimony(III) Halide-Assisted Stereospecific Coordination of Thione.

The antimony halide-aided stereospecific coordination of a cyclic thiourea-type of ligand is observed for the first time. The antimony(III) imidazole thione complexes syn-[(L1 )SbCl3 ] (syn-1) and anti-[(L1 )SbBr3 ] (anti-2) have been synthesized in very good yield by the reaction between the spatially defined steric impact ligand [(IPaul)S] (L1 ) ([(IPaul)S]=1,3-bis(2,4-methyl-6-diphenyl phenyl)imidazole thione) and corresponding antimony halide. The stereoselective formation of complexes syn-1 and anti-2 has been confirmed by both NMR and single-crystal X-ray diffraction studies. Interestingly the stereospecific nature of syn-1 and anti-2 remains intact in solution. Furthermore, the thermal stability of antimony(III) imidazole thione complexes were examined by TGA analysis.

Rare antimony(III) imidazole selone complexes: steric controlled structural and bonding aspects.

Novel antimony(iii) imidazole selone complexes in a super crowded environment are reported for the first time. The super bulky selone antimony complexes, [{IPr*Se}(SbCl3)2] (1) and [{IPr*Se}(SbBr3)2] (2), were isolated from the reactions between IPr*Se (IPr*Se = [1,3-bis(2,6-diphenylmethylphenyl)imidazole selone]) and suitable antimony(iii) halides. 1 and 2 are dinuclear complexes with a Sb : Se ratio of 1 : 0.5 with an unusual coordination mode of selone. The molecules 1 and 2 consist of both Menshutkin-type Sbπaryl interactions and a Sb-Se coordination bond. However, the reaction between antimony(iii) halides and [(IPaul)Se] ([(IPaul)Se] = [1,3-bis(2,4-methyl-6-diphenyl phenyl)imidazole selone]) with a spatially defined steric impact gave the dinuclear complex [{(IPaul)Se}(SbCl3)]2 (3) and the mononuclear complex [{(IPaul)Se}(SbBr3)] (4) without Menshutkin-type interactions. The Sb : Se ratio in 3 and 4 is 1 : 1. Interestingly, the Menshutkin-type interaction was absent in 3 and 4 due to the efficient coordinating ability of the ligand [(IPaul)Se] with the Sb(iii) center compared to that of the super bulky ligand IPr*Se. The thermal property of these antimony selone complexes was also investigated. Density functional theory (DFT) calculations were carried out on the model systems [L(SbCl3)2] (1A), [L(SbCl3)] (1B), [L'(SbCl3)2] (1C), and [L'(SbCl3)] (1D), where L = [1,3-bis(2,6-diisopropyl-4-methyl phenyl)imidazole selone] and L' = [1,3-bis(phenyl)imidazole selone], to understand the nature of orbitals and bonding situations. The computed metrical parameters of 1A are in good agreement with the experimental values. Natural population analysis of the model system reveals that the natural charge and total population of antimony(iii) are comparable. The unequal interaction between selenium and antimony obtained using Wiberg bond indices (WBIs) is fully consistent with the findings of the single-crystal X-ray studies.