Halogenation of tellurium by SO2Cl2. Formation and crystal structures of (H3O)[Te3Cl13]·1/2SO2, [(C4H8O)2H][TeCl5]·(C4H8O), [(Me2SO)2H]2[TeCl6], and [Ni(NCCH3)6][Te2Cl10]
The halogenation of elemental tellurium with SO2Cl2 in various solvents in the presence of adventitious water leads to facile formation of anionic Te(IV) species. (H3O)[Te3Cl13]·1/2SO2, [(C4H8O)2H][TeCl5]·(C4H8O), and [(Me2SO)2H2[TeCl6] were obtained in CS2, THF, and THF/DMSO, respectively. In acetonitrile in the presence of metallic nickel [Ni(NCCH2)6][Te2Cl10] is formed.
Introduction
Chalcogen dihalides EX2(E=S, Se, Te; X=Cl, Br, I) are useful reagents for synthetic applications. Of the chalcogen dihalogenides SCl2 is most stable and can be prepared from the elements or by chlorination of S2Cl2 [1], [2]. While SeCl2 is stable only in the gas phase [3], [4], [5], it survives sufficiently long in coordinating solvents to serve as a synthon [6]. At 25 °C it can be stored for hours, and the appearance of Se2Cl2 and SeCl4 due to disproportionation is only observed by 77Se NMR after 24 h. SeBr2 can be obtained by halogen exchange between SeCl2 and Me3SiBr, but disproportionation to Se2Br2 is apparent already after 1 h [6].
Tellurium dichloride has been known for over 100 years [7], but only few synthetic routes for the compound have been reported [8], [9], [10]. The reaction between TeCl4 and neat hexamethyldisilane seems to be most promising [10]. In CS2 solution, however, the formation of polymeric (MeTeCl3)n was observed [11]. TeCl2 is only stable in the gas phase and the condensation leads to rapid disproportionation to tellurium and TeCl4 [12].
In this work we report the investigation of the reaction of elemental tellurium and SO2Cl2 in various solvents in order to explore the plausibility to produce TeCl2 for synthetic applications. It turned out that in the presence of adventitious water tellurium is easily oxidized to the oxidation state IV with the production of a number of anionic species. The products have been characterized by 125Te NMR and X-ray crystallography.
Section snippets
General
All reactions were carried out under an argon atmosphere passed through P4O10. Tellurium (Aldrich), nickel (Merck), and SO2Cl2 (Aldrich) were used without further purification. DMSO (Lab-Scan) was dried by stirring over CaH2 and acetonitrile (Lab-Scan) by distillation over CaH2 before use. THF (Lab-Scan) and CS2 (Merck) were dried by distillation over Na/benzophenone and P4O10, respectively.
Spectroscopy
All 125Te NMR spectra were recorded on a Bruker DPX 400 spectrometer at 300 K operating at 126.241 MHz.
General
While SeCl2 can conveniently be prepared in coordinating solvents from elemental selenium and SO2Cl2 [6], the attempts to treat elemental tellurium with SO2Cl2 resulted in the production of chloridotellurate anions in which tellurium is in the oxidation state IV. The reaction route depends on the reaction conditions and is also influenced by the presence of adventitious water. All syntheses are reproducible.
The main products are (H3O)[Te3Cl13]·1/2SO2 (1) and [(C4H8O)2H][TeCl5]·(C4H8O) (2) in CS2
Supplementary material
Crystallographic information for 1 (excluding tables of structure factors) has been deposited with the Fachinformationzentrum Karlsruhe (FIZ) as supplementary publication number CSD 412153, and that for 2, 3, and 4 with the Cambridge Crystallographic Data Center as supplementary publication numbers CCDC 171280-171282, respectively. Copies of the data can be obtained free of charge on application to FIZ, abt. PROKA, 76344 Eggenstein-Leopoldshafen, Germany (tel.: +49-7247-808-205; e-mail:
Acknowledgements
Financial support from the Academy of Finland is gratefully acknowledged.
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