• The population of Ti species having stereo-controlling ligands increased with the surface coverage. However, the increment was far more efficient in the presence of IDs, due to the preferential formation of the special surface motifs. The nature of the stereo-controlling ligands was also quite different with and without IDs. Labile (i.e., less effective) Cl -anions were the main ligands for the ID-free system, while IDs themselves or bridged Cl -anions became the main ones for the ID-containing systems.