Uchida Daichi, Yukimoto Mariko, Tokitoh Norihiro, Yamauchi Mitsuaki, Yamada Hiroko, Mizuhata Yoshiyuki
Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.
Angew Chem Int Ed Engl. 2025 Aug 18;64(34):e202508927. doi: 10.1002/anie.202508927. Epub 2025 Jun 30.
We report the properties and reactivity of an unprecedented methylene-bridged 1,3-bis(germylene) derivative. In the solid state, it undergoes dimerization to afford a 1,2,4,5-tetragermacyclohexa-1,4-diene derivative (GeCHD). Moreover, theoretical calculations on GeCHD reveal σ*-π interactions between the two π orbitals (Ge═Ge) and the CH σ* orbital. This interaction is confirmed by a significant red shift in the solid-state UV-vis spectrum. In contrast to the behavior in the solid state, the GeCHD derivative dissociates in solution into a methylene-bridged 1,3-bis(germylene) derivative. The resultant 1,3-bis(germylene) derivative reacted with S to form a novel cage compound containing three S and two Ge atoms. On the other hand, in the reaction with triphenylphosphine sulfide, the in situ generated 2-thia-1,3-digermabicyclo[1.1.0]butane derivative activated the benzene solvent, leading to the formation of a [2 + 2] cycloaddition product. Additionally, the 1,3-bis(germylene) derivative reacted with 4-dimethylaminopyridine (DMAP) to form a three-membered ring. Its structural parameters and the results of theoretical calculations indicated the zwitterionic character.
我们报道了一种前所未有的亚甲基桥连的1,3-双（锗烯）衍生物的性质和反应活性。在固态下，它会发生二聚反应，生成一种1,2,4,5-四锗杂环己-1,4-二烯衍生物（GeCHD）。此外，对GeCHD的理论计算揭示了两个π轨道（Ge═Ge）与CH σ轨道之间的σ-π相互作用。这种相互作用通过固态紫外-可见光谱中的显著红移得到证实。与固态下的行为不同，GeCHD衍生物在溶液中会解离成亚甲基桥连的1,3-双（锗烯）衍生物。生成的1,3-双（锗烯）衍生物与S反应，形成一种含有三个S和两个Ge原子的新型笼状化合物。另一方面，在与三苯基膦硫化物的反应中，原位生成的2-硫杂-1,3-二锗双环[1.1.0]丁烷衍生物活化了苯溶剂，导致形成一种[2 + 2]环加成产物。此外，1,3-双（锗烯）衍生物与4-二甲氨基吡啶（DMAP）反应，形成一个三元环。其结构参数和理论计算结果表明了两性离子特征。
