Weak Pnictogen Bond with Bismuth: Experimental Evidence Based on Bi-P Through-Space Coupling.
Réka MokraiJamie BarrettDavid C ApperleyAndrei S BatsanovZoltán BenkőDominikus HeiftPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2019)
To study pnictogen bonding involving bismuth, flexible accordion-like molecular complexes of the composition [P(C6 H4 -o-CH2 SCH3 )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, 209 Bi-31 P through-space coupling (J=2560 Hz) is observed in solid-state 31 P NMR spectra, which is so far unprecedented in the literature, delivering direct information on the magnitude of this pnictogen interaction.
Keyphrases
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