Two equivalents of LGa (L=HC[C(Me)N(2,6-iPr C H )] ) reacted with PX (X=Cl, Br) with insertion into two P-X bonds and formation of [L(X)Ga] PX (X=Cl 1, Br 2), whereas the analogous reaction with AsCl occurred with twofold insertion and subsequent elimination of LGaCl and formation of the Ga-substituted diarsene [L(Cl)Ga] As (3). Analogous findings were observed in the reactions with Me NAsCl , yielding the unsymmetrically-substituted diarsene [L(Cl)Ga]As=As[Ga(NMe )L] (4). The reaction of As(NMe ) with LGa gave [L(Me N)Ga] As (5) after heating at 165 °C for five days, whereas the reaction with LAl gave [L(Me N)Al] As (6) after heating at only 80 °C for one day. Finally, two equivalents of LGa reacted with Bi(NEt ) to give [L(Et N)Ga] Bi (7). Complexes 1-7 were characterized by NMR spectroscopy ( H, C, P), 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.

[Cp*Sb] (Cp*=C Me ) reacts with [L Mg] and L Ga with formation of [(L Mg) (μ ,η -Sb )] (L =iPr NC[N(2,6-iPr C H )] , 1) and [(L Ga) (μ,η -Sb )] (L =HC[C(Me)N(2,6-iPr C H )] , 2). The cleavage of the Sb-Sb and Sb-C bonds in [Cp*Sb] are the crucial steps in both reactions. The formation of 1 occurred by elimination of the Cp* anion and formation of Cp*MgL , while 2 was formed by reductive elimination of Cp* and oxidative addition of L Ga to the Sb unit. 1 and 2 were characterized by heteronuclear NMR spectroscopy and single-crystal X-ray diffraction, and their bonding situation was studied by quantum chemical calculations.