The Fr-Raman spectra of a series of mechanically prepared MgCl2-TiCl4 samples with increasing content of TiCl4 have been recorded. Raman scattering lines in the range 600-100 cm(-1) reveal the formation of TiCl4 molecules complexed on the lateral cuts of activated MgCl2 crystals. This pattern of lines suggests that atleast three types of complexes are formed during the grinding process and their relative concentration depend on the starting concentration of TiCl4. Two types of these complexes have been shown to be unstable and easily removed when the samples are washed with n-hexane. In the former two cases TiCl4 Molecules are seemingly physisorbed and/or weakly complexed on MgCl2. The remaining complex is stable and it is found in every sample also after washing. This stable complex shows Raman lines which can be interpreted as originated from the complexed TiCl4 molecules with the Ti atoms in an octahedral coordination. On the other hands also monomeric TiCl4 species complexed along the (1 1 0) lateral cut or dimeric TiCl4 species complexed along the (1 0 0) lateral cuts of the MgCl2 crystal can take up a geometry with the Ti in an octahedral coordination. Both these structures have been considered in this work. Calculated Raman spectra, molecular energy considerations and Raman lines intensity ratios strongly support the fact that the stable complexes are the monomeric TiCl4 species complexed along the (1 1 0) MgCl2 lateral cuts. A spectroscopic quantitative determination of the complexed TiCl4 for this class of material is proposed. (c) 2006 Elsevier B.V. All rights reserved.