Synthesis and Characterization of Neutral Ligand α-Diimine Complexes of Aluminum with Tunable Redox Energetics

The synthesis and full characterization of a series of neutral ligand α-diimine complexes of aluminum are reported. The compounds [Al(L_Ar)₂Cl₂)][AlCl₄] [L_Ar = N, N'-bis(4-R-C₆H₄)-2,3-dimethyl-1,4-diazabutadiene] are structurally analogous, as determined by multinuclear NMR spectroscopy and solid-state X-ray diffraction, across a range of electron-donating [R = Me (2), ^tBu (3), OMe (4), and NMe₂ (5)] and electron-withdrawing [R = Cl (6), CF₃ (7), and NO₂ (8)] substituents in the aryl side arm of the ligand. UV-vis absorption spectroscopy and electrochemistry were used to access the optical and electrochemical properties, respectively, of the complexes. Both sets of properties are shown to be dependent on the R substituent. Density functional theory calculations performed on the [Al(L_Ph)₂Cl₂)][AlCl₄] complex (1) indicate primarily ligand-based frontier orbitals and were used to help support our discussion of both the spectral and electrochemical data. We also report the reaction of the L_Ph ligand with both AlBr₃ and AlI₃ and demonstrate a different reactivity profile for the heavier halide relative to the lighter members of the group.