Tweaking the Charge Transfer: Bonding Analysis of Bismuth(III) Complexes with a Flexidentate Phosphane Ligand

Réka Mokrai; Jamie Barrett; David C Apperley; Zoltán Benkő; Dominikus Heift

doi:10.1021/acs.inorgchem.0c00734

Tweaking the Charge Transfer: Bonding Analysis of Bismuth(III) Complexes with a Flexidentate Phosphane Ligand

Inorg Chem. 2020 Jul 6;59(13):8916-8924. doi: 10.1021/acs.inorgchem.0c00734. Epub 2020 Jun 12.

Authors

Réka Mokrai¹, Jamie Barrett², David C Apperley², Zoltán Benkő¹, Dominikus Heift²

Affiliations

¹ Budapest University of Technology and Economics, H-1111 Budapest, Hungary.
² Department of Chemistry, Durham University, DH1 3LE Durham, United Kingdom.

Abstract

To account for the charge transfer and covalent character in bonding between P and Bi centers, the electronic structures of [P(C₆H₄-o-CH₂SCH₃)₃BiCl_n]^(3-n)+ (n = 0-3) model species have been investigated computationally. On the basis of this survey a synthetic target compound with a dative P→Bi bond has been selected. Consecutively, the highly reactive bismuth cage [P(C₆H₄-o-CH₂SCH₃)₃Bi]³⁺ has been accessed experimentally and characterized. Importantly, our experiments (single-crystal X-ray diffraction and solid-state NMR spectroscopy) and computations (NBO and AIM analysis) reveal that the P···Bi bonding in this trication can be described as a dative bond. Here we have shown that our accordion-like molecular framework allows for tuning of the interaction between P and Bi centers.