Abstract
The reaction of tellurium tetrahalides with natural rubber parallels closely reactions with model compounds such as cyclohexene and 2-methyl- pent-2-ene carried out under similar conditions. In both cases an α-elimination reaction of an ‘organic halide’ with deposition of elemental tellurium is a dominant process, but some evidence for cross- linking of natural rubber is obtained. If methyl cyanide is the solvent for cyclohexene, or if a nitrile rubber is used, elimination of tellurium is inhibited. Tellurium tetrachloride enhances the rate and density of cross-link formation when added to tetramethylthiuram disulphide (TMTD) based natural rubber vulcanisates, but this effect is negated in the presence of triphenylphosphine. TeCl 4 reacts with TMTD to eliminate an atom of sulphur and to form a complex of tetramethylthiuram monosulphide (TMTM) viz. [Te(TMTM)Cl 4]. Corresponding bromo- and iodo-complexes have been prepared, the iodo- complex is a 1:1 electrolyte. 125Te Mössbauer data for the complexes are briefly discussed. Further reactions of the complexes are described which lead to the formation of: [Te(TMTM)Cl 2(O)(pyridine)], [Te(TMTM)X 2(O)] (X=Br, I), and [Cu(TMTM) 2] [TeCl 5] 2. Organyltellurium(IV) trihalides also react with TMTD to release sulphur and give complexes of TMTM, i.e. [( p-EtO·C 6H 4)Te- X 3] 2(TMTM) (X=Cl, Br, I).
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