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O-atom exchange between H2O and CO2 mediated by a bis(dithiolene)tungsten complex
1Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States.
Inorganic Chemistry
|July 28, 2012
Summary
A novel tungsten bis(dithiolene) complex mimics carbonic anhydrase activity. This complex facilitates carbon dioxide conversion, showing potential for CO2 reduction and carbon capture applications.
Area of Science:
- Inorganic Chemistry
- Bioinorganic Chemistry
- Organometallic Chemistry
Background:
- Tungsten-dependent formate dehydrogenases (W-FDHs) exhibit CO2 reductase activity.
- Understanding the catalytic mechanisms of W-FDHs is crucial for developing artificial CO2 reduction systems.
Purpose of the Study:
- To synthesize and characterize a reduced tungsten bis(dithiolene) complex as a model for W-FDH active sites.
- To investigate the reactivity of this model complex with carbon dioxide (CO2).
Main Methods:
- In situ hydrolysis of a W(IV) precursor to generate a reduced W-FDH model complex.
- Reaction of the model complex with CO2 at room temperature.
- Isotopic labeling experiments to trace oxygen atom incorporation.
Main Results:
- Formation of a W(IV) oxo species ([W(IV)(O)(S2C2Ph2)2](2-)) from the reaction with CO2.
- Subsequent oxidation to a W(V) oxo species ([W(V)(O)(S2C2Ph2)2](-)).
- Incorporation of the oxygen atom from CO2 into the final tungsten complex, indicating CO2 activation.
Conclusions:
- The bis(dithiolene)tungsten complex demonstrates carbonic anhydrase-like activity.
- The complex mediates carbonation and decarboxylation reactions involving CO2.
- This study provides insights into the mechanism of CO2 reduction by tungsten complexes.
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