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 beta-diketiminate germanium(II) hydride LGeH (1) [L = HC(CMeNAr)(2), Ar = 2,6-iPr(2)C(6)H(3)] 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 LGeN(3) (3), and also the germanium(IV) diamide L'Ge(NHSiMe(3))(2) (L' = CH{(C=CH(2))(CMe)(2,6-iPr(2)C(6)H(3)N)(2)}) (4). Ketones (PhCOCF(3), 2-C(4)H(3)SCOCF(3)) and 1 generated the germanium(II) alkoxides (5-6) in high yield. The activated terminal alkyne (HC CCO(2)Me) and disubstituted alkyne (EtO(2)CC CCO(2)Et) 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)NHN CHSiMe(3) (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.