ArticleInorganic chemistry2021
Unveiling the Electronic Structure of the Bi(+1)/Bi(+3) Redox Couple on NCN and NNN Pincer Complexes.
Article in Inorganic chemistry, 2021. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 12 papers.
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12 citing papers in PubMed, 27 citations in OpenAlex.
- T-Shaped Stibenium(III) Cation: Hydrostibination Without Sb─H Bond.Angewandte Chemie (International ed. in English) · 2026Article
- The Missing Link in Ferrocenophane Chemistry: Isolation of a Carba[1]Ferrocenophane.Angewandte Chemie (International ed. in English) · 2026Article
- Phosphorescence of Heavy, T-Shaped Pnictogen Trisamides in Solution at Room Temperature in the Near-Infrared II Region.Chemistry (Weinheim an der Bergstrasse, Germany) · 2026Article
- Carbene Analogues of Group 15: Reduction of s-Hydrindacene-Based Chloropnictogenium Ions To Access an Antimony Hydride Monocation and a Trinuclear Bismuth Dication.Journal of the American Chemical Society · 2026Article
- Ambiphilic Reactivity and Switchable Methyl Transfer at a T-Shaped Bi(NNN) Complex Enabled by a Redox-Active Pincer Ligand.Journal of the American Chemical Society · 2026Article
- Steric Pruning Unlocks Hierarchical Structuring, Thermochromism, C-H/O Activation, and 6-electron Redox Transmetalation in Planar Bismuth Triamides.Angewandte Chemie (International ed. in English) · 2026Article
- A Crystalline Bismuth(II) Radical Anion: Synthesis, Characterization, and Reactivity.Angewandte Chemie (International ed. in English) · 2025Article
- Rationalizing Spin-Crossover Properties of Substituted Fe (II) Complexes.Inorganic chemistry · 2025Article
- Cooperativity of Electron Transfer Coupled Spin Transitions in a Tetranuclear Fe/Co Prussian Blue Analogue Revealed by Ultrafast Spectroscopy.Angewandte Chemie (International ed. in English) · 2025Article
- Hexaphenyl-1,2-Diphosphonium Dication [PhJournal of the American Chemical Society · 2025Article
- Combining geometric constraint and redox non-innocence within an ambiphilic PBiP pincer ligand.Chemical science · 2024Article
- Planar bismuth triamides: a tunable platform for main group Lewis acidity and polymerization catalysis.Chemical science · 2023Article
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Authors and funding
4 authors at 2 institutions in 2 countries.
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No grant is acknowledged in the PubMed record.
Abstract
Low-valent group 15 compounds stabilized by pincer ligands have gained particular interest, given their direct access to fine-tune their reactivity by the coordination pattern. Recently, bismuth has been employed in a variety of catalytic transformations by taking advantage of the (+1/+3) redox couple. In this work, we present a detailed quantum-chemical study on the electronic structure of bismuth pincer complexes from two different families, namely, bis(ketimine)phenyl (NCN) and triamide bismuthinidene (NNN). The use of the so-called effective oxidation state analysis allows the unambiguous assignation of the bismuth oxidation state. In contrast to previous studies, our calculations suggest a Bi(+1) assignation for NCN pincer ligands, while Bi(+3) character is found for NNN pincer complexes. Notably, regardless of its oxidation state, the central bismuth atom disposes of up to two lone pairs for coordinating Lewis acids, as indicated by very high first and second proton affinity values. Besides, the Bi-NNN systems can also accommodate two Lewis base ligands, indicating also ambiphilic behavior. The effective fragment orbital analysis of Bi and the ligand allows monitoring of the intricate electron flow of these processes, revealing the noninnocent nature of the NNN ligand, in contrast with the NCN one. By the dissection of the electron density into effective fragment orbitals, we are able to quantify and rationalize the Lewis base/acid character.
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