Synthesis and chemistry of aryloxygermylene-amine complexes

The synthesis of stable monomeric dimesityloxygermylene-amine (MesO)₂Ge-NR₃ [NR₃ = Et₂NH, (C₆H₁₁)₂NH, Et₃N, dabco, tmeda] and chloromesityloxygermylene-amine MesO(Cl)Ge-tmeda complexes is presented. All compounds have been fully characterized by spectroscopic methods. The insertion reaction of (MesO)₂Ge-tmeda 1a with dimethyl disulfide, bis(trimethylsilyl)peroxide and iodomethane is reported. Cycloaddition reactions with dimethylbutadiene are especially effective without any activation and with dimethyl acetylenedicarboxylate led selectively to compounds 7 and 8. In the latter case, the transient formation of a germirene has been evidenced by a trapping reaction. The structures of 3, 7 and 8 were determined by single-crystal X-ray diffraction.