Abstract
AbstractUsing the chelating C,C′‐bis(silylenyl)‐ortho‐dicarborane ligand, 1,2‐(RSi)2‐1,2‐C2B10H10 [R=PhC(NtBu)2], leads to the monoatomic zero‐valent Ge complex (“germylone”) 3. The redox non‐innocent character of the carborane scaffold has a drastic influence on the reactivity of 3 towards reductants and oxidants. Reduction of 3 with one molar equivalent of potassium naphthalenide (KC10H8) causes facile oxidation of Ge0 to GeI along with a two‐electron reduction of the C2B10 cluster core and subsequent GeI‐GeI coupling to form the dianionic bis(silylene)‐supported Ge2 complex 4. In contrast, oxidation of 3 with one molar equivalent of [Cp2Fe][B{C6H3(CF3)2}4] as a one‐electron oxidant furnishes the dicationic bis(silylene)‐supported Ge2 complex 5. The Ge0 atom in 3 acts as donor towards GeCl2 to form the trinuclear mixed‐valent Ge0→GeII←Ge0 complex 6, from which dechlorination with KC10H8 affords the neutral Ge2 complex 7 as a diradical species.
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