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Controlling the Redox Speciation of N,C,N-Bi Complexes Using the Anion Coordination Index
Vanessa A Béland1, Alexios G Stamoulis1, Nils Nöthling1
1Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, Mülheim an der Ruhr 45470, Germany.
Organometallics
|April 17, 2026
Summary
The stability of bismuth pincer complexes depends on anion coordination. Coordinating anions trigger disproportionation of Bi-(II) complexes, while noncoordinating anions stabilize them, impacting bismuth redox chemistry.
Area of Science:
- Organometallic Chemistry
- Inorganic Chemistry
- Catalysis
Background:
- N,C,N-bismuth pincer complexes exhibit diverse redox chemistry.
- This chemistry is crucial for various catalytic organic reactions.
- Systematic study of redox speciation stability is lacking.
Purpose of the Study:
- To investigate the thermodynamic stability of dimeric N,C,N-Bi-(II) pincer complexes.
- To understand the influence of anion coordinating ability on bismuth redox states.
- To elucidate the disproportionation behavior of low-valent bismuth species.
Main Methods:
- Cyclic voltammetry to probe redox potentials and stability.
- Spectroscopic characterization (e.g., NMR, UV-Vis) of reaction products.
- Crystallographic analysis to determine structures of bismuth complexes.
Main Results:
- Dimeric N,C,N-Bi-(II) pincer complexes are stable with noncoordinating anions (α ≤ -0.4).
- Complexes disproportionate to Bi-(I) and Bi-(III) species in the presence of coordinating anions (α ≥ 1).
- An intermediate range of coordinating ability (α between -0.4 and 1) requires excess electrolyte for disproportionation.
Conclusions:
- Anion coordinating ability is a critical factor controlling bismuth pincer complex redox stability.
- Disproportionation is a key pathway for low-valent bismuth speciation.
- Findings provide a deeper understanding of bismuth redox manifolds for catalytic applications.
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