کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1326799 | 977445 | 2010 | 8 صفحه PDF | دانلود رایگان |

Room temperature oxidative addition of α-bromo-2-acetylthiophene to elemental tellurium and aryltellurium(II) bromide provides direct routes to (2-thiophenoylmethyl)tellurium(IV) dibromides, (2-(C4H3S)COCH2)2TeBr2 (1b) and 2-(C4H3S)COCH2ArTeBr2 (Ar = 1-C10H7, Npl, 2b; 2,4,6-Me3C6H2, Mes, 3b). The chloro analogues, 2-(C4H3S)COCH2ArTeCl2 (Ar = Npl, 2a; Mes, 3a) were prepared by the condensation reaction of the parent methyl ketone with NplTeCl3 or MesTeCl3. Metathesis of these products with an alkali iodide affords the iodo analogues 1c, 2c and 3c. These diorganotellurium dihalides are reduced with aqueous bisulfite to diorganotellurides 1–3, which can be oxidized readily with dihalogens to the desired diorganotellurium(IV) dihalides. Compound 1 is a rare example of a symmetrical telluroether with Csp3–Te–Csp3 grouping that has been characterized by single-crystal diffraction techniques. Preference of the 2-thiophenoylmethyl ligand for small-bite (C, O) chelation over less strained (C, S) coordination is evident in the crystal structures of the Te(IV) compounds 1b, 2a, 2b and 3a. The unexpected transoidal orientation of the two acylmethyl ligands in the solid state molecular configuration of symmetrical diorganotellurium(IV) dibromide 1b appears to be a combined effect of electronic repulsion due to the thiophene moieties and steric repulsion of bromo ligands.
Room temperature oxidative addition of α-bromo-2-acetylthiophene to Te0 and [ArTeIIBr] affords (2-thiophenoylmethyl)tellurium(IV) dibromides. The unexpected transoidal orientation of the two acylmethyl ligands in the symmetrical diorganotellurium(IV) dibromide highlights the substantial role of electronic factors of ligands. In its crystal lattice, centrosymmetric dimmers formed via reciprocatory Te⋯Br interactions are identified.Figure optionsDownload as PowerPoint slide
Journal: Journal of Organometallic Chemistry - Volume 695, Issue 23, 1 November 2010, Pages 2532–2539