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.