Stabilized Germylenes Based on Diethylenetriamines and Related Diamines: Synthesis, Structures, and Chemical Properties

Abstract 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(SiMe 3 ) 2 ] 2 with various diamines ( 1a – 1e ) or by the metathesis reaction of [GeCl 2 · 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, 1 H and 13 C NMR spectroscopy, and X‐ray diffraction analysis (germylenes 2b , 2i , 2j , Ge 4+ compounds 5b , 7a , 7b , 8 , 10 , 11 ). All the synthesized germylenes are monomeric.