PUB - Publikationen an der Universität Bielefeld

N,N-Diisopropylaminomethyllithium (1) was prepared by transmetalation from (Me3SnCH2NPr2)-Pr-i and n-BuLi. It was characterized by NMR spectroscopy (H-1, C-13, Li-7). Compound 1 crystallizes as a hexamer ((LiCH2NPr2)-Pr-i)(6) and allowed the determination of the first solvent-free structure of an alpha-lithiated amine. It contains a Li-6 core (distorted octahedron) 6-fold capped by (CH2NPr2)-Pr-i units. 1 is very sensitive to air-oxidation. A partially [(LiCH2NiPr2)(4)-(LiOCH2NiPr2)(2) (2)] and a completely oxidized [((LiOCH2NPr2)-Pr-i)(6) (3)] cluster compound could be isolated. 2 and 3 were characterized by multinuclear NMR spectroscopy and by single-crystal X-ray diffraction. The results show that the hexameric structure is retained upon partial or complete oxidation. 1 was used as aminomethylating agent and reacted with Me2AlCl and Me2GaCl to give the aminomethylaluminum and -gallium compounds ((Me2MCH2NPr2)-Pr-i)(2) (M = Al, Ga), which are dimers containing six-membered rings. They were characterized by elemental analyses, NMR spectroscopy, and crystal structure determinations. They are present as dimers containing six-membered M2C2N2 rings in solution and in the solid state.