Activation of heteroallenes by metal-substituted electron-rich tetrylenes

The metal-substituted germylene LGa(mu-Cl)GeDMP (L = HC[C(Me)NDipp]2, Dipp = 2,6-iPr2C6H3, DMP = 2,6-Mes2C6H3, Mes = 2,4,6-Me3C6H2) 1 reacts with CO2 with reductive decarbonylation and formation of the oxygen-bridged complex L(Cl)GaOGeDMP 2, which was also formed in the reaction of 1 with N2O. The CO2 reaction most likely proceeds via intermediate formation of a gallacarboxylate germylene complex as is observed in reactions of complex 1 with both ethyl isocyanate and N,N'-dicyclohexylcarbodiimide, yielding the corre-sponding heteroallenes insertion complexes L(Cl)Ga-[C(NEt)O]-GeDMP 3 and L(Cl)Ga-[C(NCy)2]-GeDMP 4. In addition, the gallanediyle stannylene adduct LGa-Sn[N(SiMe3)(Dipp)] 5 reacts with CO2 to form the gallacarboxylate tin complex L(Cl)Ga-(CO2)-Sn[N(Dipp)(SiMe3)] 6. Complexes 2-4 and 6 are characterized spectroscopically (1H, 13C, 119Sn (6), IR) and by single crystal X-ray diffraction (sc-XRD).