Changing the Reactivity of Zero‐ and Mono‐Valent Germanium with a Redox Non‐Innocent Bis(silylenyl)carborane Ligand
Shenglai Yao, Arseni Kostenko, Yun Xiong, Christian Lorent, Aleš Růžička, Matthias Drieß
Abstract
Abstract Using the chelating C,C′‐bis(silylenyl)‐ortho‐dicarborane ligand, 1,2‐(RSi) 2 ‐1,2‐C 2 B 10 H 10 [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 (KC 10 H 8 ) causes facile oxidation of Ge 0 to Ge I along with a two‐electron reduction of the C 2 B 10 cluster core and subsequent Ge I ‐Ge I coupling to form the dianionic bis(silylene)‐supported Ge 2 complex 4 . In contrast, oxidation of 3 with one molar equivalent of [Cp 2 Fe][B{C 6 H 3 (CF 3 ) 2 } 4 ] as a one‐electron oxidant furnishes the dicationic bis(silylene)‐supported Ge 2 complex 5 . The Ge 0 atom in 3 acts as donor towards GeCl 2 to form the trinuclear mixed‐valent Ge 0 →Ge II ←Ge 0 complex 6 , from which dechlorination with KC 10 H 8 affords the neutral Ge 2 complex 7 as a diradical species.