Synthesis and Structural Characterization of the novel T‐shaped Organotellurium(II) Dihalides (PyH)[mesTeClBr] and (PyH)[mesTeX₂] (Py = pyridine; mes = mesityl; X = Cl, Br)

Abstract

Abstract(MesTe)2 and bromine or chlorine react with pyridinium bromide and pyridinium chloride to give (PyH)[mesTeBr2] (1), (PyH)[mesTeClBr] (2) and (PyH)[mesTeCl2] (3), respectively. The TeII atoms in 1, 2 and 3 adopt a three‐coordinate, T‐shaped configuration and the trans tellurium‐halogen bonds present different distances, since the X(1)‐halogens {Br (1), Cl (2, 3)} attain hydrogen bondings toward the N–H group of the pyridinium cations. The title compounds do not reproduce the dimeric assembling of some newly reported parent tellurium dihalides.

Synthesis and structural features of new aryltellurenyl iodides

“…The complex (PyH)[tmpTeI 3 (I 3 )] (4) represents a rare example of Te IV compound in which a I À 3 chain appears as component of the complex and not as solvate, as normally occurs [1,5]. The reciprocal association of single [tmpTeI 3 12-membered rings with an inversion center, as shown in Fig.…”

“…Almost as a rule, tellurium(II) and tellurium(IV) iodide compounds attain all possible combinations of secondary, interionic interactions. Single monomers and dimers and also polymeric chains attaining 1D, 2D and 3D networks, as well as rare polymeric structures with chalcogen atoms presenting mixed-valence states are often described [3,4], like, for example, the recently reported [5] neutral species [mesTeI(l 3 -I)(TeImes) 2 ] n (mes = 2,4,6-trimethylphenyl). The chemical and structural versatility of organyltellurenyl iodides, combined with the noticeable effect of the ligand R on the stabilization of mixed-valent aryltellurenyl iodides, led us to the development of functionalized organic substituents to stabilize Te centers in uncommon and useful assemblies.…”

“…Former studies [7] on the influence of the substituent R on the controlled oxidation of the Te atom have shown that the aryltellurenyl iodides ArTeI can be viewed also as key compounds in the syntheses of Te II and Te IV products. Since the mesityl group allows the stabilization of tellurium(II) iodides as mesTeI [5,8,9], the possibility of using mesTeI as a selective oxidation reagent has been studied and demonstrated also in the case of the preparation of the mixed-valent complex [RTeTeI 2 R] (R = 2,6-dimethoxiphenyl) [7]. As part of our research on further effects of the ligand R on the stabilization and structure of aryltellurenyl iodides, we describe in this work the syntheses and the structural characterization of the intermediary [tmpTeI] 2 6 ]ÁI 2 (7) (tmp = 2,3,5,6-tetramethylphenyl).…”

Uncommon assembling of organotellurium iodides: Synthesis and X-ray characterization of [mesTeI(μ-I)2(TeImes)2]n, (C5H6N)4[mesTeI2]2(I3)2 and {(C5H6N)3[(mesTeI3)(μ-I−)(TeI3mes)](I3)2}n (mes=2,4,6-trimethylphenyl)

“…TeÁ Á Áp-aryl interactions have not been detected, differently of earlier reported organochalcogen halides of tellurium II [2]. The synthesis and the X-ray characterization of the series (PyH)[mesTeBr 2 ], (PyH) [mesTeClBr] and (PyH)[mesTeCl 2 ] were also further reported [3], but these compounds do not reproduce the assembling of the above mentioned parent dihalides, e. g., there is no dimeric association of the anions. Nevertheless, the secondary NHÁ Á ÁX bonds of the anionic moieties toward the pyridinium cations are also evident.…”

Innovative synthetical and structural features of new aryltellurenyl iodides

“…It is well known that uncommon compositions and configurations are characteristic for these species [1,2], since tellurium(II) and tellurium(IV) iodide compounds are able to attain all possible combinations of secondary, interionic interactions. Single monomers and dimers, but also polymeric chains attaining 1D, 2D and 3D networks, as well as rare polymeric structures with chalcogen atoms presenting mixed-valence states are often described [3,4], like, for example, the reported [5] neutral complex polymer [mesTeI(m 3 -I) (TeImes) 2 ] n (mes ¼ 2,4,6-trimethylphenyl). The chemical and structural versatility of organyltellurenyl iodides, combined with the remarkable effect of the ligand R on the stabilization of mixed-valent aryltellurenyl iodides, led us to the development of functionalized organic substituents to stabilize Te centers in uncommon and useful assemblies.…”