Molecular and crystal structures of TeCl4-allylalcohol and -allylacetate adducts

1,2-electrophilic addition of TeCl4 to the C=C bond of allylalcohol is obse rved, while with allylacetate, 1,3-addition occurs, due to migration of the acetate group. The allylalcohol adduct comprises two different kinds of mo lecules in the solid state, Cl3Te[CH2CH(CI)CH2OH -->] and Cl2Te[CH2CH(Cl)CH 2O-], with dative Te <--O and covalent Te-O bonds, five-membered ring struc tures and Cl-Te...Cl and O-H...O bridges linking the different molecules. I n the allylacetate adduct. Cl3Te[CH2CH(CH2Cl)OC(CH3)=O -->], a six-membered ring is formed via an intramolecular dative Te <--O interaction, the molec ules being linked via C-Cl...Te bridges. Multinuclear NMR spectroscopy and H-1-H-1-NOESY combined with ab initio (MP2/LANL2DZP) geometry optimisation show the geometry of the ring structures in solution to be similar to those in the solid state.