Hardy Matthias, Engeser Marianne, Lützen Arne
University of Bonn, Kekulé-Institute of Organic Chemistry and Biochemistry, Gerhard-Domagk-Str. 1, D-53121 Bonn, Germany.
Beilstein J Org Chem. 2020 Nov 3;16:2701-2708. doi: 10.3762/bjoc.16.220. eCollection 2020.
Employing 4-ethynylaniline as a simple organic ligand we were able to prepare the stable -bis(acetylide)platinum(II) complex [Pt(L)(PBu)] as a linear metalloligand. The reaction of this metalloligand with iron(II) cations and pyridine-2-carbaldehyde according to the subcomponent self-assembly approach yielded decanuclear heterobimetallic tetrahedron FePt(L). Thus, combination of these two design concepts - the subcomponent self-assembly strategy and the complex-as-a-ligand approach - ensured a fast and easy synthesis of large heterobimetallic coordination cages of tetrahedral shape with a diameter of more than 3 nm as a mixture of all three possible -, - and -symmetric diastereomers. The new complexes were characterized by NMR and UV-vis spectroscopy and ESI mass spectrometry. Using GFN2-xTB we generated energy-minimized models of the diastereomers of this cage that further corroborated the results from analytical findings.
我们以4-乙炔基苯胺作为一种简单的有机配体,成功制备了稳定的双(乙炔基)铂(II)配合物[Pt(L)(PBu)]作为线性金属配体。根据亚组分自组装方法,该金属配体与铁(II)阳离子和吡啶-2-甲醛反应,得到了十核异双金属四面体FePt(L)。因此,这两种设计概念——亚组分自组装策略和配合物作为配体的方法——相结合,确保了快速简便地合成直径超过3 nm的大型四面体异双金属配位笼,该笼是所有三种可能的 -、 - 和 - 对称非对映异构体的混合物。通过核磁共振、紫外-可见光谱和电喷雾电离质谱对新配合物进行了表征。使用GFN2-xTB,我们生成了该笼非对映异构体的能量最小化模型,进一步证实了分析结果。