Stabilized germylenes based on diethylenetriamines and related diamines: Synthesis, structures, and chemical properties
A series of novel, low‐valent germanium compounds 2a–2j based on four diethylenetriamines 1a–1d, (methyl)bis(pyrrol‐2‐ylmethyl)amine (1e), N,N′‐(sulfanediyldibenzene‐2,1‐diyl)bis(pentafluoroaniline) (1f), N,N′‐(oxydibenzene‐2,1‐diyl)bis(pentafluoroaniline) (1g), and (pentafluorophenyl)amines 1i and 1j have been obtained either by the reaction of Ge[N(SiMe3)2]2 with various diamines (1a–1e) or by the metathesis reaction of [GeCl2·dioxane] with lithium amides. The oxidative insertion (with halogenation reagents, MeI, disulfides), [1+4] cycloaddition, and oxidation reactions of the synthesized germylenes were investigated. The compositions and structures of the novel compounds were established by elemental analysis, 1H and 13C NMR spectroscopy, and X‐ray diffraction analysis (germylenes 2b, 2i, 2j, Ge4+ compounds 5b, 7a, 7b, 8, 10, 11). All the synthesized germylenes are monomeric.
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