Synthesis of aluminium complexes bearing a piperazine-based ligand system

Aluminium complexes bearing the N,N-chelating ligand 1,4-bis(2-hydroxy-3,5-di-tert-butyl)piperazine (1) have been synthesised. Both monometallic and bimetallic aluminium methyl complexes (2 and 3, respectively) were prepared by treatment of 1 with the appropriate amount of AlMe3. Complex 2 can be converted to 3 by addition of excess AlMe3. Bimetallic aluminium-ethyl complex 4 was also prepared. Treatment of 1 with AlEt2Cl afforded the monometallic chloride complex 5. Treatment of this latter complex with potassium alkoxides (KOR, R = Me, Et, iPr, tBu) or AgOTf afforded the corresponding aluminium alkoxide complexes (6, R = Et; 7, R = Me; 8, R = iPr; 9, R = tBu; 10, R = OTf) in good yields. Aluminium ethoxide complex 6 was also synthesised by treatment of 1 with AlEt2OEt. All of these complexes were tested as potential catalysts in the ring-opening polymerisation of rac-lactide and caprolactone with limited success.

Graphical abstractAluminium complexes bearing the N,N-chelating ligand 1,4-bis(2-hydroxy-3,5-di-tert-butyl)piperazine have been synthesised. Both monometallic and bimetallic aluminium alkyl complexes have been generated, with the bimetallic species more stable in solution. A series of monometallic aluminium alkoxide complexes has also been synthesised.Figure optionsDownload full-size imageDownload as PowerPoint slide