Weak Pnictogen Bond with Bismuth: Experimental Evidence Based on Bi-P Through-Space Coupling
Weak Pnictogen Bond with Bismuth: Experimental Evidence Based on Bi-P Through-Space Coupling
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DOI：
10.1002/chem.201900266
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发表时间：
2019-03-15
影响因子：
4.3
通讯作者：
Heift, Dominikus
中科院分区：
文献类型：
--
作者：
Mokrai, Reka;Barrett, Jamie;Heift, Dominikus
为了研究含铋的烟原键合，合成了具有弹性的手风琴状分子配合物[P(C6H4-o-CH2SCH3)(3)BiX3], （X=Cl, Br， I）。单晶x射线衍射分析、DFT和从头计算证实，铋和P中心之间的弱静电相互作用的强度很大程度上取决于铋上卤素取代基的性质。值得注意的是，在固态P-31核磁共振光谱中观察到Bi-209-P-31通过空间耦合（J=2560 Hz），这是迄今为止文献中前所未有的，提供了关于这种烟原相互作用程度的直接信息。
To study pnictogen bonding involving bismuth, flexible accordion-like molecular complexes of the composition [P(C6H4-o-CH2SCH3)(3)BiX3], (X=Cl, Br, I) have been synthesised and characterised. The strength of the weak and mainly electrostatic interaction between the Bi and P centres strongly depends on the character of the halogen substituent on bismuth, which is confirmed by single-crystal X-ray diffraction analyses, DFT and ab initio computations. Significantly, Bi-209-P-31 through-space coupling (J=2560 Hz) is observed in solid-state P-31 NMR spectra, which is so far unprecedented in the literature, delivering direct information on the magnitude of this pnictogen interaction.