AbstractIn main group chemistry, the BDI ligand ([HC(C(Me)N(R))2]), more commonly known as NacNac, has proved indispensable over the last two decades. Within this work, we are introducing the hybrid NacNac‐akin ligand 3,3‐dimethyl‐2‐[2‐methyl‐2‐(2,6‐diisopropyl‐aniline)ethenyl]‐3H‐indolenine (DNI). On the basis of this novel ligand, alkali metal complexes [DNI(M1)] [M1=Li (3(OEt2)), Na (4(THF)3), and K (5(THF)3)] have been synthesized by facile deprotonation of the ligand's backbone. The reaction of DNI with AlH3 ⋅ NMe2Et led to the aluminium dihydride compound [DNI‐AlH2] (6) in excellent yield (90 %). Further synthesis of [DNI‐AlI2] (7), which is seen as a potential precursor for the aluminium(I) complex, was realized in the presence of 1.0 equiv. iodine with 6. All products 2–7 were completely characterized by 2D‐NMR, mass spectrometry, elemental analysis and SC‐XRD. Density functional theory calculations were performed to provide better understanding of their bonding characteristics and electronic structures.