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.

Department of Chemistry Metalorganics and Inorganic Materials Technische Universität Berlin Strasse des 17 Juni 135 Sekr C2 10623 Berlin Germany

Department of Chemistry Physical and Biophysical Chemistry Technische Universität Berlin Strasse des 17 Juni 135 Sekr PC14 10623 Berlin Germany

Department of General and Inorganic Chemistry Faculty of Chemical Technology University of Pardubice Studentska 573 53210 Pardubice Czech Republic

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Deposition Numbers 2070702 (3), 2070706 (4), 2070703 (5), 2070704 (6) and 2070705 (7) contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service www.ccdc.cam.ac.uk/structures. DOI

Access to cationic polyhedral carboranes via dynamic cage surgery with N-heterocyclic carbenes