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Triple the fun: tris(ferrocenyl)arene-based gold(i) complexes for redox-switchable catalysis
Axel Straube1, Peter Coburger1, Luis Dütsch2
1Institute of Inorganic Chemistry, Universität Leipzig Johannisallee 29 D-04103 Leipzig Germany hey@uni-leipzig.de https://anorganik.chemie.unileipzig.de/de/anorganik/ak-hey-hawkins/.
Chemical Science
|June 7, 2021
Summary
Researchers synthesized novel C3-symmetric tris(ferrocenyl)arene-based tris-phosphanes and their gold(i) complexes. These complexes exhibit tunable electrochemical properties and cooperative catalytic behavior, with stepwise rate control achieved through controlled oxidation.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Electrochemistry
Background:
- Development of C3-symmetric ligands for fine-tuning metal complex properties.
- Exploration of cooperative effects in multinuclear metal catalysts.
- Application of ferrocene derivatives in electrochemistry and catalysis.
Purpose of the Study:
- To synthesize and characterize novel C3-symmetric tris(ferrocenyl)arene-based tris-phosphanes and their gold(i) complexes.
- To investigate the electrochemical properties and catalytic activity of these complexes.
- To explore the influence of oxidation state on catalytic performance.
Main Methods:
- Modular synthesis of C3-symmetric tris-phosphanes and their gold(i) complexes.
- Electrochemical characterization to determine oxidation potentials.
- Catalytic evaluation in the ring-closing isomerization of N-(2-propyn-1-yl)benzamide.
- In situ and ex situ oxidation studies using a ferrocenium oxidant.
Main Results:
- Successful synthesis of C3-symmetric tris(ferrocenyl)arene-based tris-phosphanes and their homotrinuclear gold(i) complexes.
- Demonstration of tunable electrochemical responses by modifying the arene core.
- Observation of cooperative catalytic behavior in gold(i) complexes, outperforming mononuclear counterparts.
- Stepwise modulation of catalytic rates through controlled addition of an oxidant.
- Structural characterization of the tri-oxidised benzene-based complex, confirming the P-Au-Cl motif integrity.
Conclusions:
- C3-symmetric tris(ferrocenyl)arene scaffolds provide a versatile platform for designing electrochemically tunable gold(i) catalysts.
- Cooperative effects in homotrinuclear gold(i) complexes enhance catalytic activity.
- Controlled oxidation offers a precise method for tuning catalytic rates in these systems.
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