Tungsten Biscorroles: New Chiral Sandwich Compounds
Tungsten Biscorroles: New Chiral Sandwich Compounds
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DOI：
10.1002/chem.201504848
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发表时间：
2016-05-10
影响因子：
4.3
通讯作者：
Ghosh, Abhik
中科院分区：
文献类型：
--
作者：
Alemayehu, Abraham B.;Vazquez-Lima, Hugo;Ghosh, Abhik
氧化金属化方法涉及回流十氢萘中游离碱中位三芳基可咯和W（CO）（6）的相互作用，产生了一组三种钨（VI）双可咯，这是第一种涉及可咯的同配夹心化合物。两个配合物的单晶X-射线结构显示正方形反棱柱配位和强烈的圆顶coroles与长W-N距离为2.15-2.22埃和一个实质性的位移约1.17埃的金属相对于平均N-4平面的配体。该结构对应于近似C-2对称性，因此是手性的。密度泛函理论计算表明，对映异构体的构型稳定，因此适合手性拆分。它们的其他显着特性包括在（357 +/- 2）nm处的强烈蓝移Soret带，在（781 +/- 3）nm处的相对强烈的W（dz 2）近红外特征，以及约1.3V的低电化学HOMO-LUMO间隙。本文所获得的结果表明，metallobiscoroles可能会出现作为一类新的固有的手性发色团与新的光学和电化学性能。
The oxidative metalation method, involving the interaction of free-base meso-triarylcorroles and W(CO)(6) in refluxing decalin, led to a set of three tungsten(VI) biscorroles, the first homoleptic sandwich compounds involving corroles. Single-crystal X-ray structures of two of the complexes revealed square-antiprismatic coordination and strongly domed corroles with long W-N distances of 2.15-2.22 angstrom and a substantial displacement of approximate to 1.17 angstrom of the metal relative to the mean N-4 planes of the ligands. The structures correspond to approximate C-2 symmetry and are thus chiral. DFT calculations strongly indicate that the enantiomers are configurationally stable and hence amenable to chiral resolution. Their other notable properties include a strongly blueshifted Soret band at (357 +/- 2)nm, a relatively intense W(dz2 ) near-IR feature at (781 +/- 3)nm, and a low electrochemical HOMO-LUMO gap of approximately 1.3V. The results obtained herein suggest that metallobiscorroles may emerge as a new class of inherently chiral chromophores with novel optical and electrochemical properties.