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

ABSTRACT: 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 Ge^I along with a two-electron reduction of the C₂ B₁₀ cluster core and subsequent Ge^I -Ge^I 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 →Ge^II ←Ge⁰ complex 6, from which dechlorination with KC₁₀ H₈ affords the neutral Ge₂ complex 7 as a diradical species.

SUBMITTER: Yao S 

PROVIDER: S-EPMC8252802 | biostudies-literature | 2021 Jun

REPOSITORIES: biostudies-literature