Weak pnictogen bond with bismuth: Experimental evidence based on Bi-P through-space coupling

Mokrai, Réka; Barrett, Jamie; Apperley, David; Batsanov, Andrei; Benkő, Zoltán; Heift, Dominikus

Abstract

To study pnictogen bonding involving bismuth, flexible accordion‐like molecular complexes of the composition [P(C6H4‐o‐CH2SCH3)3BiX3], (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, 209Bi–31P through‐space coupling (J=2560 Hz) is observed in solid‐state 31P NMR spectra, which is so far unprecedented in the literature, delivering direct information on the magnitude of this pnictogen interaction.

Citation

Mokrai, R., Barrett, J., Apperley, D., Batsanov, A., Benkő, Z., & Heift, D. (2019). Weak pnictogen bond with bismuth: Experimental evidence based on Bi-P through-space coupling. Chemistry - A European Journal, 25(16), 4017-4024. https://doi.org/10.1002/chem.201900266

• Journal Article Type: Article
• Online Publication Date: Jan 24, 2019
• Publication Date: Mar 15, 2019
• Deposit Date: Feb 20, 2019
• Publicly Available Date: Mar 14, 2019
• Journal: Chemistry - A European Journal
• Print ISSN: 0947-6539
• Electronic ISSN: 1521-3765
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 25
• Issue: 16
• Pages: 4017-4024
• DOI: https://doi.org/10.1002/chem.201900266
• Public URL: https://durham-repository.worktribe.com/output/1302724