Barium tetraalkylaluminate complexes supported by the super-bulky hydrotris(pyrazolyl)borate ligand

Abstract

A heteroleptic barium aminobenzyl complex [(Tp^Ad,iPr)Ba(o-CH₂C₆H₄-NMe₂)] (1) was obtained in excellent yield from a simple one-pot reaction. Treatment of [(Tp^Ad,iPr)Ba(o-CH₂C₆H₄-NMe₂)] (1) with two equivalents of AlR₃ (R = Me, Et) led to the formation of barium tetraalkylaluminate complexes [(Tp^Ad,iPr)Ba(AlR₄)]_n (R = Me, n = 2, 2; R = Et, n = 1, 3) as dimers or monomers in the solid state. The Tp^Ad,iPr ligand-free peralkylated barium complex [Ba(AlEt₄)₂]_n was isolated by the addition of ten equivalents of AlEt₃ under the same conditions. The donor-induced aluminate cleavage is not applicable when donor solvents are added to complexes 2 and 3. In the solution of complexes 2 and 3, the alkylaluminate moieties and Tp^Ad,iPr ligands show a rapid fluxional behavior in [D₈]toluene solution over the temperature range of −70 to 25 °C, without any significant decoalescence of the corresponding proton signals.