Synthesis, Structure, and Reactivity of Ga‐Substituted Distibenes and Sb‐Analogues of Bicyclo[1.1.0]butane

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