Reactivity of germanium(II) hydride with nitrous oxide, trimethylsilyl azide, ketones, and alkynes and the reaction of a methyl analogue with trimethylsilyl diazomethane

Abstract

The reactions of stable β-diketiminate germanium(II) hydride LGeH (1) [L = HC(CMeNAr)₂, Ar = 2,6-iPr₂C₆H₃] with nitrous oxide, trimethylsilyl azide, ketones, and alkynes are described. 1 reacts with nitrous oxide to yield the germanium(II) hydroxide LGeOH (2), and with trimethylsilyl azide affords in toluene at room temperature the germanium(II) azide LGeN₃ (3), and also the germanium(IV) diamide L′Ge(NHSiMe₃)₂ (L′ = CH{(CCH₂)(CMe)(2,6-iPr₂C₆H₃N)₂}) (4). Ketones (PhCOCF₃, 2-C₄H₃SCOCF₃) and 1 generated the germanium(II) alkoxides (5–6) in high yield. The activated terminal alkyne (HCCCO₂Me) and disubstituted alkyne (EtO₂CCCCO₂Et) react with 1 to form the germanium(II) substituted alkenes (vinyl germylene) (7–8). Further reaction of the methylgermanium(II) compound LGeMe (9) with trimethylsilyl diazomethane resulted in the formation of germanium(IV) amide L′Ge(Me)NHNCHSiMe₃ (10). Compounds 2–8, and 10 were characterized by microanalysis and multi-nuclear NMR spectroscopy. Furthermore compounds 3–6, and 8 are confirmed by X-ray structural analysis.