Two equivalents of LGa (L=HC[C(Me)N(2,6-iPr2C6H3)]2) reacted with PX3 (X=Cl, Br) with insertion into two P−X bonds and formation of [L(X)Ga]2PX (X=Cl 1, Br 2), whereas the analogous reaction with AsCl3 occurred with twofold insertion and subsequent elimination of LGaCl2 and formation of the Ga-substituted diarsene [L(Cl)Ga]2As2 (3). Analogous findings were observed in the reactions with Me2NAsCl2, yielding the unsymmetrically-substituted diarsene [L(Cl)Ga]As=As[Ga(NMe2)L] (4). The reaction of As(NMe2)3 with LGa gave [L(Me2N)Ga]2As2 (5) after heating at 165 °C for five days, whereas the reaction with LAl gave [L(Me2N)Al]2As2 (6) after heating at only 80 °C for one day. Finally, two equivalents of LGa reacted with Bi(NEt2)3 to give [L(Et2N)Ga]2Bi2 (7). Complexes 1–7 were characterized by NMR spectroscopy (1H, 13C, 31P), elemental analysis, and single-crystal X-ray diffraction (except for 1 and 5). The bonding situations in 4, 6, and 7 were analyzed by quantum chemical calculations.