A General Route to Metal-Substituted Dipnictenes of the Type [L(X)M] E.

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.