Krebs Kilian M, Hanselmann Dominik, Schubert Hartmut, Wurst Kai, Scheele Marcus, Wesemann Lars
Institut für Anorganische Chemie , Eberhard Karls Universität Tübingen , Auf der Morgenstelle 18 , 72076 Tübingen , Germany.
Institut für Physikalische und Theoretische Chemie , Eberhard Karls Universität Tübingen , Auf der Morgenstelle 18 , 72076 Tübingen , Germany.
J Am Chem Soc. 2019 Feb 27;141(8):3424-3429. doi: 10.1021/jacs.8b13645. Epub 2019 Feb 13.
An intramolecular germylene-phosphine Lewis pair (1) was reacted with germanium dichloride to give in 92% yield a phosphine adduct of a chloro substituted germyl-germylene (2). After reduction of this dichloride with strong reductants like the Mg(I) reagent {(Nacnac)Mg} (72% yield) or Na (52% yield) a phosphine stabilized digermavinylidene (3) was isolated as crystalline material [Nacnac = {[(Mes)NC(Me)]CH}, Mes = 2,4,6-MeCH]. The electronic structure of the digermavinylidene was investigated by density functional theory calculations. In reaction with adamantylphosphaalkyne the product of a [2+2] cycloaddition was characterized (4). Adamantylazide abstracts at room temperature a germanium atom from the digermavinylidene and a tetrameric organogermanium nitride (5) was isolated as colorless crystals.
分子内的亚锗烯 - 膦路易斯对（1）与二氯化锗反应，以92%的产率得到氯取代的亚锗基 - 亚锗烯的膦加合物（2）。用强还原剂如Mg（I）试剂{（Nacnac）Mg}（产率72%）或Na（产率52%）还原该二氯化物后，分离出膦稳定的二锗亚乙烯基（3）作为晶体材料[Nacnac = {[（Mes）NC（Me）]CH}，Mes = 2,4,6 - MeCH]。通过密度泛函理论计算研究了二锗亚乙烯基的电子结构。与金刚烷基磷炔反应时，表征了[2 + 2]环加成产物（4）。在室温下，金刚烷基叠氮化物从二锗亚乙烯基中夺取一个锗原子，分离出无色晶体的四聚有机锗氮化物（5）。
