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

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

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)3BiCln](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.

Citation

Mokrai, R., Barrett, J., Apperley, D. C., Benkő, Z., & Heift, D. (2020). Tweaking the Charge Transfer: Bonding Analysis of Bismuth(III) Complexes with a Flexidentate Phosphane Ligand. Inorganic Chemistry, 59(13), 8916-8924. https://doi.org/10.1021/acs.inorgchem.0c00734

• Journal Article Type: Article
• Online Publication Date: Jun 12, 2020
• Publication Date: Jul 6, 2020
• Deposit Date: Jun 15, 2020
• Publicly Available Date: Jun 18, 2020
• Journal: Inorganic Chemistry
• Print ISSN: 0020-1669
• Electronic ISSN: 1520-510X
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 59
• Issue: 13
• Pages: 8916-8924
• DOI: https://doi.org/10.1021/acs.inorgchem.0c00734
• Public URL: https://durham-repository.worktribe.com/output/1268760