ChemInform Abstract: Polygermanes. Part 14. Polygermanes as By‐Products in the Grignard Reaction of PhMgBr with GeCl₄.

Abstract

Die bei der Grignard‐Reaktion von Phenylmagnesiumbromid (I) mit dem Germaniumchlorid (II) als Nebenprodukte entstehenden Germane (V) und (VI) werden isoliert, gereinigt und charakterisiert.

Synthetic, Structural, and Physical Aspects of Organo-Oligogermanes

“…[12] ORGANO- OLIGOGERMANES 75 functional theory, and these data are collected in Table 4. [9] The UV= visible maxima for 27 and 29 were observed at 233 and 228 nm, respectively, and the oxidation potentials for these two species are 1435 (27) and 1921 (29). Therefore, the experimental data indicate that the HOMO -LUMO gap in 29 is larger than that in 27, and also that the HOMO for 29 is stabilized relative to that for 27.…”

“…This type of reactivity has not been realized for silicon or tin. Although a significant number of oligogermanes have been prepared using these methods, [29, these synthetic methods are typically complicated by low yields and=or the formation of mixtures of products. The separation of these product mixtures is not trivial since the oligogermanes are sensitive to both air and moisture, and therefore the separations must be conducted under an inert atmosphere of nitrogen or argon.…”

“…Synthetic methods for the preparation of oligomeric germanium compounds have included Wurtz-type coupling of organogermanium halides by alkali metals, [28] the action of Grignard or organolithium reagents on organogermanium halides, [29] mercuration=demurcuration of organogermanes, [30,31] and nucleophilic substitution reactions involving triorganogermanium anions and organogermanium halides. [32] The latter process is somewhat unique to germanium chemistry as the triorganogermanium anions employed are prepared via the abstraction of hydrogen from triorganogermanium hydrides using organolithium reagents.…”