Xiong Yun, Chen Dandan, Yao Shenglai, Zhu Jun, Ruzicka Ales, Driess Matthias
Metalorganics and Inorganic Materials, Department of Chemistry, Technische Universität Berlin, Straße des 17, Juni 135, Sekr. C2, 10623 Berlin, Germany.
State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China.
J Am Chem Soc. 2021 Apr 28;143(16):6229-6237. doi: 10.1021/jacs.1c01722. Epub 2021 Apr 14.
The first Ge(0)-Ge(II) germylone-germylene-paired Ge complex (L)Ge () and the molecular Ge cluster (L)Ge () supported by the chelating carbanionic -,'-dicarborandiyl-silylene ligand L [L = ,'-CBH, = PhC(BuN)Si] have been synthesized and isolated via reduction of the corresponding precursors chlorogermyl-germyliumylidene chloride (), [(L)Ge(Cl)Ge]Cl, and (L)GeCl () with CK, respectively. The latter precursors were obtained from the unexpected outcome of the reaction of the -,'-dicarborandiyl phosphine-silylene ligand L () { = P[N(Bu)CH]} and GeCl·dioxane. Compound is formed in higher yields (65% yields) by the salt metathesis reaction of the -lithium dicarborandiyl-'-silylene salt L () [ = Li(OEt)] with GeCl·dioxane. The molecular structures of all these species (-) have been established and confirmed spectroscopically and crystallographically. The electronic structures of and were elucidated by density functional theory calculations. While possesses a localized dative Ge(0)→Ge(II) bond, the Ge-Ge σ bonds in are delocalized in the Ge cluster core. Featuring a donor-acceptor interaction between two chelating silylenes and the Ge core, compound represents a unique molecular model for a Ge cluster.
首个锗（0）-锗（II）亚锗烯-锗烯配对的锗配合物（L）Ge（）以及由螯合碳负离子 -,'-二碳硼烷基-亚硅基配体L [L =,'-CBH, = PhC(BuN)Si] 支撑的分子锗簇（L）Ge（），已分别通过用CK还原相应前体氯锗基-锗亚甲基氯化物（）、[(L)Ge(Cl)Ge]Cl和（L）GeCl（）而合成并分离出来。后一种前体是由 -,'-二碳硼烷基膦-亚硅基配体L（）{ = P[N(Bu)CH]}与GeCl·二氧六环反应的意外产物得到的。化合物 通过 -锂代二碳硼烷基-'-亚硅基盐L（）[ = Li(OEt)]与GeCl·二氧六环的盐复分解反应以较高产率（65%产率）形成。所有这些物种（-）的分子结构已通过光谱和晶体学方法确定并证实。 和 的电子结构通过密度泛函理论计算得以阐明。虽然 具有局域化的给体-受体Ge(0)→Ge(II)键，但 中的Ge-Ge σ键在锗簇核心中是离域的。化合物 具有两个螯合亚硅基与锗核心之间的给体-受体相互作用，代表了一种独特的锗簇分子模型。
