Ligand (biochemistry)

Pathology

Chalcogen

Receptor

Organic chemistry

Reactivity (psychology)

Carborane

Crystallography

Medicinal chemistry

Inorganic chemistry

Chemistry

Alternative medicine

Silylene

Silicon

Germanium

Biochemistry

Redox

Medicine

Photochemistry

Angewandte Chemie International Edition

Using the chelating C,C'-bis(silylenyl)-ortho-dicarborane ligand, 1,2-(RSi)2 -1,2-C2 B10 H10 [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 (KC10 H8 ) causes facile oxidation of Ge0 to GeI along with a two-electron reduction of the C2 B10 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 [Cp2 Fe][B{C6 H3 (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 KC10 H8 affords the neutral Ge2 complex 7 as a diradical species.

Changing the Reactivity of Zero‐ and Mono‐Valent Germanium with a Redox Non‐Innocent Bis(silylenyl)carborane Ligand