Dichlorogermylene-dioxane complex

The first member of the new class of stable radicals, (t-Bu2MeSi)3Si 43, was synthesized by the one-electron oxidation of the silylsodium derivative (t-Bu2MeSi)3SiNa with dichlorogermylene-dioxane complex GeCl2 diox in Et20 (Scheme 2.35). ... 

The synthesis of the first cyclotrisilenes has required a longer time than for the cyclotrigermenes due to the lack of suitable stable silylenes, in contrast, for example, to the well-known dichlorogermylene-dioxane complex . Therefore, the preliminary preparation of the silylene precursors, which can generate silylenes in situ, was necessary for the successful synthesis of cyclotrisilenes. Until now, only two examples of cyclotrisilenes have been reported in the literature, of which only one was structurally characterized. 

The mechanism of the formation of a three-membered unsaturated ring was clarified later, when this reaction was reexamined by the same authors in detail . They found that the reaction of dichlorogermylene-dioxane complex with one equivalent of f-BusSiNa in THF at —78 °C led to the formation of c ,frawi-l,2,3-trichloro-l,2,3-tris(tri-terf-butylsilyl)cyclotrigermene 7 in 98% yield (Scheme 4). The cis,trails conformation of 7 was established by NMR spectroscopy and X-ray analysis (Figure 3). Treatment of 7 with two equivalents of f-Bu3SiNa in TFIF at —78°C cleanly produced cyclotrigermene 5 (Scheme 4), which gives evidence that 7 is a precursor for 5. 

The insertion reaction can be easily modeled by using the dioxane complex of dichlorogermylene24,49. Kinetic investigation of the reaction with benzyl chloride was carried out50. The experimental data were in line with kinetic equation 9, which involves participation of a free dichlorogermylene in the insertion step (in dioxane solution, where the equilibrium is shifted to the left, the insertion reaction does not occur). 

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