Oxidative Addition of Group 13 and 14 Metal Halides and Alkyls to Ga(DDP) (DDP = Bulky Bisimidinate)

The oxidative addition of a variety of group 13 and group 14 halides and alkyls RaMX to the mono valent group 13 bis-imidinate Ga(DDP) (DDP = 2-{(2,6-diisopropyl-phenyl)amino}−4-{(2,6-diisopropylphenyl)imino}−2-pentene) is reported. Accordingly, the insertion of Ga(DDP) into the Ga-Me bond of GaMe3 yield in the complexes [{(DDP)GaMe}GaMe2] (1) and [{(DDP)GaMe}2GaMe] (2), respectively, which show a temperature-dependent equilibrium between 1 at higher temperatures and 2 at lower temperatures. In the case of GaCl3, the only isolable product is [{(DDP)GaCl}2GaCl] (3). The related reaction of SnMe2Cl2 with Ga(DDP) yields the compound [Me2Sn{ClGa(DDP)}2] (4), whereas SnMe4 behaves inert. In the case of SiCl4, only the monoinsertion product [Cl3Si{ClGa(DDP)}] (5) was observed. Finally, [(CH3)3C{ClGa(DDP)}] (6) is synthesized by insertion of Ga(DDP) into the C−Cl bond of ClC(CH3)3. All new compounds were fully characterized by elemental analysis, NMR-spectroscopy, and single-crystal X-ray diffraction analysis.