Sodium cation migration above the diimine π-system of solvent coordinated dpp-BIAN sodium aluminum complexes (dpp-BIAN=1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene)

The reactions of the disodium salt of the 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) ligand with one equivalent of Me2AlCl in diethyl ether, toluene, and benzene produced the complexes [Na(Et2O)(2)(dpp-BIAN) AlMe2] (1), [Na(eta(6)-C7H6)(dpp-BIAN)AlMe2] (2) and [Na(eta(6)-C6H6)(dpp-BIAN)AlMe2] (3), respectively. Recrystallization of 1 from hexane afforded solvent-free [{Na(dppBIAN)AlMe2}(n)] (4) or [Na(Et2O)(dpp-BIAN)AlMe2] (5) depending on the temperature of the solvent. The molecular structures of 1-5 have been determined by single-crystal X-ray diffraction. The sodium cation coordinates either one of the naphthalene rings (1) or the diimine part of the dpp-BIAN ligand (2-5). In the complexes 2 and 3, the sodium cation additionally coordinates the toluene (2) or benzene molecule (3) in an eta(6)-fashion.