Tellurium derivatives of 3-acetyl-2,5-dimethylthiophene: Synthetic and structural aspects

Oxidative addition of α-bromo-3-acetyl-2,5-dimethylthiophene to elemental tellurium and aryltellurium(II) bromide provides direct routes to (2,5-dimethyl-3-thiophenoylmethyl)tellurium(IV) dibromides, (Me2TpnCOCH2)2TeBr2 (1a; Me2Tpn = 2,5-Me2-3-C4HS) and Ar(Me2TpnCOCH2)TeBr2 (Ar = 1-C10H7, Npl, 2a; 2,4,6-Me3C6H2, Mes, 3a). The chloro analogs of 2a and 3a, Ar(Me2TpnCOCH2)TeCl2 (Ar = Npl, 2b; Mes, 3b) and derivative when Ar = Anisyl (anisyl = 4-MeOC6H4, 4b) were prepared by the condensation reaction of methyl ketone, Me2TpnCOCH3 with NplTeCl3, MesTeCl3 and anisylTeCl3 respectively while the chloro analog of 1a, bis(2,5-dimethyl-3-thiophenoylmethyl)tellurium(IV) dichloride, (Me2TpnCOCH2)2TeCl2 (1b) was obtained by the condensation reaction of methyl ketone, Me2TpnCOCH3 with TeCl4. Metathesis of these products (1a–b, 2a–b, 3a–b and 4b) with an alkali iodide affords the iodo analogs 1c, 2c, 3c and 4c. These diorganotellurium dihalides are reduced with aqueous bisulfite to diorganotellurides 1–4, which can be oxidized readily with dihalogens to the desired diorganotellurium(IV) dihalides. The crystal structures of the Te(IV) compounds 1b, 2a, 3c and 4b have been studied and all the Te(IV) compounds, the carbonyl functionalized organic moiety, show intramolecular 1,4–Te⋯O secondary bonding interaction (SBI). In the crystal lattice of 2a, the intermolecular Te⋯Br secondary bonding interactions are evident and result in a dimer. They get further associated via C–H⋯Br secondary interactions to form a 3D supramolecular motifs. In 1b, 3c and 4b supramolecular motifs are formed through C–H⋯O and C–H⋯Cl interactions.