Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Institute for Sustainable Chemistry and Catalysis with Boron, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074, Würzburg, Germany.
Angew Chem Int Ed Engl. 2017 Jan 16;56(3):889-892. doi: 10.1002/anie.201609601. Epub 2016 Dec 20.
Unsaturated bridges that link the two cyclopentadienyl ligands together in strained ansa metallocenes are rare and limited to carbon-carbon double bonds. The synthesis and isolation of a strained ferrocenophane containing an unsaturated two-boron bridge, isoelectronic with a C=C double bond, was achieved by reduction of a carbene-stabilized 1,1'-bis(dihaloboryl)ferrocene. A combination of spectroscopic and electrochemical measurements as well as density functional theory (DFT) calculations was used to assess the influence of the unprecedented strained cis configuration on the optical and electrochemical properties of the carbene-stabilized diborene unit. Initial reactivity studies show that the dibora[2]ferrocenophane is prone to boron-boron double bond cleavage reactions.
在应变的安萨茂金属配合物中，连接两个环戊二烯基配体的不饱和桥仅限于碳-碳双键。通过稳定卡宾的 1,1'-双（二卤代硼基）二茂铁的还原，合成并分离出了一种含有不饱和二硼桥的应变二茂铁烷，其与 C=C 双键等电子。通过光谱和电化学测量以及密度泛函理论（DFT）计算的组合，评估了前所未有的应变顺式构型对卡宾稳定二硼单元的光学和电化学性质的影响。初步反应性研究表明，二硼[2]茂铁烷容易发生硼-硼双键的断裂反应。
