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 Me 2 AlCl in diethyl ether, toluene, and benzene produced the complexes [Na(Et 2 O) 2 (dpp‐BIAN)AlMe 2 ] ( 1 ), [Na(η 6 ‐C 7 H 8 )(dpp‐BIAN)AlMe 2 ] ( 2 ) and [Na(η 6 ‐C 6 H 6 )(dpp‐BIAN)AlMe 2 ] ( 3 ), respectively. Recrystallization of 1 from hexane afforded solvent‐free [{Na(dpp‐BIAN)AlMe 2 } n ] ( 4 ) or [Na(Et 2 O)(dpp‐BIAN)AlMe 2 ] ( 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 η 6 ‐fashion.