Synthesis and coordination behaviour of aluminate-based quinolyl ligands

Abstract

The effects of moving the donor N-atom from the 2-position in lithium (2-pyridyl)- and (2-quinolyl)aluminates to the more remote position in (8-quinolyl)aluminates have been investigated by solid-state structural and DFT computational studies of the new complexes [{EtAl(2-qy)₃}Li(μ-X)Li(THF)₃] (X = Cl/Br 62 : 38) [(1)Li(μ-X)Li(THF)₃], [{(EtAl(2-qy)₃)Li}₂(μ-Br)]⁻Li(THF)₄⁺ [{1Li}₂(μ-Br)]⁻Li(THF)₄⁺, [{EtAl(2-Me-8-qy)₃}Li] [(2)Li], [{Me₂Al(2-Me-8-qy)₂}Li(THF)] [(3a)Li(THF)], [{Me₂Al(6-Me-2-py)₂}Li(THF)₂] [(4)Li(THF)₂] and [{{EtAl(2-Me-8-qy)₂}₂O}(Li₂THF)] (5). Increasing the remoteness of the donor N-atom from the bridgehead results in large differences in the coordination of the Li⁺ cations by the (8-quinolyl)aluminate anions compared to 2-quinolyl or 2-pyridyl counterparts. The results are of potential interest in understanding how the coordination sites of ligands of this type can be tuned for the coordination requirements of specific metal centres.