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

Dalton Transactions Pub Date: 2009-10-05 DOI: 10.1039/B914164B

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{(C[double bond, length as m-dash]CH2)(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 (HC[triple bond, length as m-dash]CCO2Me) and disubstituted alkyne (EtO2CC[triple bond, length as m-dash]CCO2Et) 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[double bond, length as m-dash]CHSiMe3 (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.

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