Synthesis and characterisation of neutral and cationic alkyl aluminium complexes bearing N,O-Schiff base chelates with pendant donor arms

Abstract

The Schiff base ligands [3,5-But2-2-(OH)C6H2CHNL] [L = CH2CH2NMe2 (1a), 2-(PhO)C6H4 (1b), 2-CH2C5H3N (1c), 8-C9H6N (quinoline) (1d) and 2-(PPh2)C6H4 (1e)] are accessed in good yields (>85%) via standard imine condensation reactions. Reaction of 1a–e with Me3Al at room temperature affords the corresponding complexes [(3,5-But2-2-(O)C6H2CHNL)AlMe2] (2a–e); in the case of L = 8-quinoline, the same reaction conducted in refluxing toluene affords binuclear {[3,5-But2-2-(O)C6H2CHMeN-8-C9H6N]AlMe}2 (3) by methyl migration from metal to ligand. Further reaction of the dimethyl compounds with B(C6F5)3 in CD2Cl2 or C6D6 affords the cationic systems [(3,5-But2-2-(O)C6H2CHNL)AlMe]+ (4a–e). The crystal structures of 2a, 2c, 2e and 3 have been determined. In 2a and 2c the respective ligands bind to the metal centre via all three heteroatoms, the aluminium having a trigonal bipyramidal geometry, whereas in 2e coordination is via nitrogen and oxygen only, and the aluminium is tetrahedral. Complex 3 has a dimeric structure with the ligand adopting both tridentate and binucleating roles; the aluminium centres are trigonal bipyramidal.