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雙卡本鉗形配位基及其對多金屬構型的配位行為

A Bis-(carbone) Pincer Ligand and Its Coordinative Behavior toward Multi-Metallic Configurations

Angew. Chem. Int. Ed. 2022, 61, e202201884
Bamlaku Semagne Aweke, Cheng-Han Yu, Minna Zhi, Wen-Ching Chen, Glenn P. A. Yap, Lili Zhao*, Tiow-Gan Ong*

Carbones are divalent carbon(0)species that contain two lone pairs of electrons. Herein, we have prepared the first known stable and isolable free bis-(carbone) pincer framework with a well-defined solid-state structure. This bis-(carbone)ligand is an effective scaffold for forming monometallic(Ni and Pd) and trinuclear heterometallic complexes with Au-Pd-Au, Au-Ni-Au, and Cu-Ni-Cu configurations. Sophisticated quantum-theoretical analyses found that the metal-metal interactions are too weak to play a significant role in upholding these multi-metallic configurations; rather, the four lone pairs of electrons within the bis-(carbone) framework are the main contributors to the stability of the complexes.

雙卡本鉗形配位基及其對多金屬構型的配位行為

卡本是含有兩對孤對電子的二配位碳零價化合物。在本研究中,我們製備了第一個穩定且可分離並具有明確晶體結構的游離雙卡本鉗形骨架。這種雙卡本配位基是形成單金屬(Ni 和 Pd)和三核異金屬 Au-Pd-Au、Au-Ni-Au 和 Cu-Ni-Cu 構型錯合物的有效支架。先進的量子理論分析發現金屬-金屬相互作用力太弱,無法在維持這些多金屬配置上發揮重要作用;相反的,雙卡本骨架內的四對孤對電子是多金屬錯合物穩定性的主要貢獻者。