Hou Yuanfeng, Li Zhongshu, Li Yaqi, Liu Peng, Su Cheng-Yong, Puschmann Florian, Grützmacher Hansjörg
Lehn Institute of Functional Materials (LIFM) , School of Chemistry , Sun Yat-Sen University , 510275 Guangzhou , China . Email:
Guangdong Engineering and Technology Research Center for Advanced Nanomaterials , School of Environment and Civil Engineering , Dongguan University of Technology , Dongguan 523808 , China.
Chem Sci. 2019 Jan 21;10(11):3168-3180. doi: 10.1039/c8sc05281f. eCollection 2019 Mar 21.
Phosphinines, as aromatic heterocycles, usually engage in coordination as η-P σ-complexes or η-phosphinine π-complexes. The μ-P bridging coordination mode is rarely observed. With the aim to study the effect of different electronic configurations of phosphinines on the coordination modes, a series of anionic phosphinin-2-olates and neutral phosphinin-2-ols were prepared with moderate to high yield. Then the coordination chemistry of these two series was studied in detail towards coinage metals (Au(i) and Cu(i)). It is observed that the anionic phosphinin-2-olates possess a higher tendency to take a bridging position between two metal centers compared to the neutral phosphinin-2-ols. Based on these experimental findings bolstered by DFT calculations, some insight is gained on how the unconventional μ-P phosphinine bridging coordination mode can be made more conventional and used for the synthesis of polynuclear complexes.
膦杂苯作为芳香杂环化合物，通常以η-P σ-络合物或η-膦杂苯π-络合物的形式参与配位。μ-P桥连配位模式很少被观察到。为了研究膦杂苯不同电子构型对配位模式的影响，制备了一系列中等至高收率的阴离子型膦杂苯-2-醇盐和中性膦杂苯-2-醇。然后详细研究了这两个系列与贵金属（Au(i)和Cu(i)）的配位化学。观察到与中性膦杂苯-2-醇相比，阴离子型膦杂苯-2-醇盐在两个金属中心之间占据桥连位置的倾向更高。基于这些由密度泛函理论（DFT）计算支持的实验结果，对于如何使非常规的μ-P膦杂苯桥连配位模式更常规化并用于多核配合物的合成有了一些认识。
