Stabilized germylenes based on dialkanolamines: Synthesis, structure, chemical properties

A series of novel low valent germanium compounds RN((CHRCRRO)-C-2-R-1-O-3)((CHRCHRO)-C-4-O-5)Ge 1-13 (R = Me, Ph, Bn; R-1, R-2, R-3, R-4, R-5 H, Me, Ph, (CH2)(3), (CH2)(4), CH2(C6H4)) was obtained via the reaction between Ge [N(SiMe3)(2)](2) and various dialkanolamines. All new compounds were characterized by elemental analysis, H-1 and C-13 NMR spectroscopy and in several cases by X-ray diffraction analysis (1, 3, 8, 10). The compounds 1, 3, 8 are dimeric in the solid state due to the formation of intermolecular Ge-O bonds, the complex 10 is monomeric, all compounds possess a transannular Ge-N bond. The reactivity of the germylenes synthesized was investigated in reactions of oxidative insertion (with halogenation reagents, MeI, disulfides), [1 + 4]-cycloaddition, oxidation and in reactions with water and acetic anhydride. Some reactions were investigated by DFT calculations. (C) 2012 Elsevier B. V. All rights reserved.