Chu Zhenwei, He Guomei, Cheng Xiaoli, Deng Zhirong, Chen Jiangxi
Department of Materials Science and Engineering, College of Materials, Xiamen University, Xiamen, 361005, P. R. China.
Angew Chem Int Ed Engl. 2019 Jul 1;58(27):9174-9178. doi: 10.1002/anie.201904815. Epub 2019 May 22.
Metalla-aromatics are important complexes that show unique properties owing to their highly conjugated systems, which show Hückel or Möbius aromaticity. Recently, several metalla-aromatics showing spiro-aromaticity or σ-aromaticity have been reported. Herein, we report the isolation of the first cyclopropametallanaphthalenes, in which the metallacyclopropene ring shows σ-aromaticity and weak hyperconjugative aromaticity. The reaction of OsCl (PPh ) with o-ethynylphenyl alkynes in the presence of PPh followed by protonation with HCl yielded the first cyclopropametallanaphthalenes. The reaction mechanism and the aromaticity were also investigated by density functional theory studies.
金属芳香化合物是一类重要的配合物，由于其高度共轭体系而表现出独特的性质，这些共轭体系具有休克尔或莫比乌斯芳香性。最近，有报道称几种金属芳香化合物具有螺芳香性或σ芳香性。在此，我们报告了首例环丙基金属萘的分离，其中金属环丙烯环表现出σ芳香性和弱的超共轭芳香性。在三苯基膦存在下，四氯合锇（OsCl₄）与邻乙炔基苯乙炔反应，然后用盐酸质子化，得到了首例环丙基金属萘。还通过密度泛函理论研究对反应机理和芳香性进行了研究。
