1-(1,3-Benzothiazol-2-ylsulfanyl)propan-2-ol (C10H10NS2OH, LH) was used as a multifunctional ligand in reactions with aluminum trialkyls R3Al (R = Bu-i, Et, Bu-t). The reactions at 1:1 M ratio of reagents proceeded with formation of dimeric (R2AlL)(2) (R = Bu-i, Et) complexes with a central Al2O2 ring, whereas in a presence of an excess of R3Al the compounds [(R2Al)(R3Al)L](2) (R = Bu-i, Et) with the central Al2O2 ring and R3Al molecules coordinated to nitrogen atoms were obtained. (Bu3Al)-Bu-i reacted with the LH yielding monomeric complex (Bu2AlL)-Bu-t independently on the molar ratio of reagents. In the compound, Al coordinates to the nitrogen atom to form intramolecular sp(2)-N donor bonding. The compounds [((Bu2Al)-Bu-i)((Bu3Al)-Bu-i)L](2) (1), (Et2AlL)(2) (2) and (Bu2AlL)-Bu-t (3) were synthesized as pure compounds and characterized. Among four heteroatoms of the ligand, only the oxygen and nitrogen atoms can form bonds with aluminum atoms, whereas two sulfur atoms are non-coordinative. The compounds 1 and 2 are active as an initiator of the e-caprolactone polymerization. (C) 2015 Elsevier Ltd. All rights reserved.