Budapest University of Technology and Economics, H-1111, Budapest, Hungary.
Department of Chemistry, Durham University, DH1 3LE, Durham, UK.
Chemistry. 2019 Mar 15;25(16):4017-4024. doi: 10.1002/chem.201900266. Epub 2019 Feb 25.
To study pnictogen bonding involving bismuth, flexible accordion-like molecular complexes of the composition [P(C H -o-CH SCH ) BiX ], (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- P through-space coupling (J=2560 Hz) is observed in solid-state P NMR spectra, which is so far unprecedented in the literature, delivering direct information on the magnitude of this pnictogen interaction.
为了研究涉及铋的类氮族键，我们合成并表征了组成式为[P(C H -o-CH SCH ) BiX ]的柔性手风琴状分子配合物（X=Cl、Br、I）。Bi 和 P 中心之间的弱且主要为静电相互作用的强度强烈依赖于铋上卤素取代基的性质，这一点通过单晶 X 射线衍射分析、DFT 和从头算计算得到了证实。值得注意的是，在固态 P NMR 光谱中观察到了显著的 Bi-P 隔空耦合（J=2560 Hz），这在文献中尚属首例，直接提供了关于这种类氮族相互作用大小的信息。
