α-Diimine ligands, in particular 1,4-diazabutadiene (dad) and bis(iminoacenaphthene) (bian) derivatives, have been widely used for coordination with various metals, including main-group, transition, and lanthanide and actinide metals. In addition to their tunable steric and electronic properties, the dad and bian ligands are redox-active and can readily accept one or two electrons, converting into the radical-anionic (L˙⁻) or dianionic (enediamido, L²⁻) form, respectively. This non-innocence brings about rich electronic structures and properties of the ligands and complexes thereof. For example, the dad ligands in their three redox levels can effectively stabilize a series of metal centers in different oxidation states, including low-valent metals. Moreover, these ligands can serve as electron reservoirs and can participate in reactions toward other molecules with or without metals. Therefore, such ligands are extremely useful in the areas of low-valent complexes and small molecule activation. Herein, we will discuss the use of dad (and bian) ligands in the stabilization of metal–metal-bonded compounds, in particular those of main-group metals, as well as small molecule activation by these (low-valent) metal coordination species where the non-innocence of the ligands plays a key role.

Dialumane can promote cyclo-trimerization of isocyanides in the presence of Na, affording the product [Na][LAl{μ-η¹:η²-(tBuNC)₃}Al(CN)L] with a unique aromatic tri(tert-butylimino)deltate dianion [C₃N₃(tBu)₃]²⁻.

The reductive coupling of carbodiimides RNCNR (R = 2,6-iPr₂C₆H₃, Cy, iPr) by using [(dpp-bian)GaNa(dme)₂] (1); [(dpp-dad)GaNa(thf)₃] (2a) and [(dpp-dad)GaK(thf)₄Ga(dpp-dad)][K(thf)₆] (2b) led to the guanidinate derivatives [(dpp-bian)Ga(NCy)₂CNCy][Na(thf)₂] (3); [LGaN(R)C(RN)N(R)C(RN)][M] L = dpp-bian, M = Na(dme)₂, R = iPr, (4a); L = dpp-dad, M = Na(thf)₃, R = iPr, (4b); R = Cy, (4c); M = K(thf)₄, (4d); L = dpp-bian, M = Na(dme)₂, R = Cy, (4e) and [(dpp-dad)Ga(2,6-iPr₂C₆H₃N)₂C][Na(thf)₂] (5).