Yao Shenglai, Kostenko Arseni, Xiong Yun, Lorent Christian, Ruzicka Ales, Driess Matthias
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.
Angew Chem Int Ed Engl. 2021 Jun 25;60(27):14864-14868. doi: 10.1002/anie.202103769. Epub 2021 Jun 1.
Using the chelating C,C'-bis(silylenyl)-ortho-dicarborane ligand, 1,2-(RSi) -1,2-C B H [R=PhC(NtBu) ], 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 H ) causes facile oxidation of Ge to Ge along with a two-electron reduction of the C B cluster core and subsequent Ge -Ge coupling to form the dianionic bis(silylene)-supported Ge complex 4. In contrast, oxidation of 3 with one molar equivalent of [Cp Fe][B{C H (CF ) } ] as a one-electron oxidant furnishes the dicationic bis(silylene)-supported Ge complex 5. The Ge atom in 3 acts as donor towards GeCl to form the trinuclear mixed-valent Ge →Ge ←Ge complex 6, from which dechlorination with KC H affords the neutral Ge complex 7 as a diradical species.
使用螯合的C，C'-双（硅亚烷基）-邻二碳硼烷配体1,2-(RSi)-1,2-C₂B₁₀H₁₀[R = PhC(NtBu)₂]，可得到单原子零价锗配合物（“锗酮”）3。碳硼烷骨架的氧化还原非无辜特性对3与还原剂和氧化剂的反应性有显著影响。用一摩尔当量的萘基钾（KC₁₀H₈）还原3会导致锗轻松氧化为Ge²⁺，同时C₂B₁₀簇核心发生两电子还原，随后发生Ge-Ge偶联形成双阴离子双（硅亚烷基）支撑的锗配合物4。相反，用一摩尔当量的[Cp₂Fe][B{C₆H₄(CF₃)₂}₄]作为单电子氧化剂氧化3，得到二阳离子双（硅亚烷基）支撑的锗配合物5。3中的锗原子作为给体与GeCl₂反应形成三核混合价态的Ge⁰→Ge²⁺←Ge⁰配合物6，用KC₁₀H₈对其进行脱氯反应可得到作为双自由基物种的中性锗配合物7。
