Stabilizing Monoatomic Two-Coordinate Bismuth(I) and Bismuth(II) Using a Redox Noninnocent Bis(germylene) Ligand
Jian Xu1, Sudip Pan2, Shenglai Yao1
1Metalorganic and Inorganic Materials, Department of Chemistry, Technische Universität Berlin, 10623 Berlin, Germany.
Journal of the American Chemical Society
|February 26, 2024
Summary
Researchers developed a stable bismuth(I) cation complex using a novel bis(germylene) ligand. This strategy allows for the isolation of challenging bismuth(I) and bismuth(II) species, offering new avenues in inorganic chemistry.
Area of Science:
- Inorganic Chemistry
- Organometallic Chemistry
- Materials Science
Background:
- Isolating low-valent bismuth (BiI, BiII) species is difficult due to bismuth's strong reducing nature.
- Stabilizing reactive metal centers often requires specialized ligand design that can accommodate charge and redox activity.
Purpose of the Study:
- To develop a strategy for stabilizing isolable monatomic BiI and BiII species.
- To synthesize and characterize novel bismuth complexes utilizing redox noninnocent ligands.
Main Methods:
- Synthesis of a novel bis(iminophosphonamido-germylene)xanthene ligand.
- Two-electron reduction of a BiIIII2 precursor using cobaltocene.
- Characterization using DFT calculations, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) spectroscopy.
- Electrochemical studies including single-electron transfer (SET) reactions.
Main Results:
- A remarkably stable BiI cation complex (4) was synthesized, featuring a novel bis(germylene) ligand.
- Charge delocalization onto the germylene moieties stabilized the BiI center, enhancing stability compared to Pb0 analogues.
- A reversible single-electron oxidation yielded an isolable BiII radical complex (5), with the unpaired electron primarily on bismuth.
- The BiI cation demonstrated high nucleophilicity, reacting with electrophiles to form BiIII complexes.
Conclusions:
- The redox noninnocent bis(germylene) ligand effectively stabilizes low-valent bismuth species (BiI and BiII).
- This approach provides a convenient route to isolable and reactive bismuth(I) and bismuth(II) complexes.
- The stabilized bismuth complexes exhibit interesting redox behavior and nucleophilicity, opening possibilities for new synthetic transformations.
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