Monovalent gallanediyl LGa {L=HC[C(Me)N(2,6‐iPr₂C₆H₃)]₂} reacts with SbX₃ to form the Ga‐substituted distibenes [(LGaX)₂Sb₂] (X=NMeEt 1, Cl 2). Upon heating, 2 reacts to the bicyclo[1.1.0]butane analogue [(LGaCl)₂(μ,η^1:1‐Sb₄)] 3 containing a [Sb₄]²⁻ dianion. Moreover, 2 reacts with Li amides LiNR₂ in salt elimination reactions that form the corresponding amido‐substituted compounds 1 and [(LGaNMe₂)₂Sb₂] 4, whereas reactions of 4 and [(LGaNMe₂)₂(μ,η^1:1‐Sb₄)] 5 with two equivalents of GaCl₃ resulted in the formation of 2 and 3, respectively. 1, 2 and 3 were characterized by ¹H and ¹³C NMR spectroscopy, elemental analysis, and single crystal X‐ray diffraction. In addition, their bonding situation was analyzed by quantum chemical calculations.

Dedication to Prof. D. Naumann on the occasion of his 75th birthday.