A series of new titanium isopropoxide complexes (1-4-Ti(O(i)Pr)(2) based on enantiopure (1-H(2)), racemic (2-H(2)), meso (3-H(2)) and diastereomeric (4-H(2)) aminodiol ligands have been prepared and tested as initiators for the ring opening polymerization (ROP) of L/rac-lactide in solution and in bulk conditions. All complexes were shown to have significant activity in solution at 70 degrees C and higher activity in bulk at 130 degrees C with a good control over the molar mass distribution and molecular weights. The complex derived from the racemic-aminodiol ligand gave partially heterotactic polylactide in ROP of rac-lactide and afforded atactic polylactide in the bulk, whereas all other complexes yielded atactic polylactides both in solution and in bulk. Ligand variation (chirality) in the complexes has little effect on either the activity or selectivity of the initiators. The polymerization kinetics using (1-Ti(O(i)Pr)(2)) as an initiator indicated a first order reaction with respect to the monomer concentration. (C) 2011 Elsevier Ltd. All rights reserved.