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Classical Gold Carbonyl Complexes in Tetrahedral and Trigonal-Planar Settings
Mukundam Vanga1, Alvaro Muñoz-Castro2, H V Rasika Dias1
1Department of Chemistry and Biochemistry, The University of Texas at Arlington, Arlington, TX 76019, United States.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|November 6, 2023
Summary
Researchers synthesized a unique gold(I)-carbonyl complex using a tris(pyridyl)borate ligand. This study explored coinage metal trends and revealed significant gold-to-carbon π-back-bonding, lowering the carbon-oxygen bond strength.
Area of Science:
- Organometallic Chemistry
- Inorganic Chemistry
- Coordination Chemistry
Background:
- Gold(I) complexes are valuable in catalysis and materials science.
- Understanding metal-ligand bonding is crucial for designing new complexes.
- Tris(pyridyl)borate ligands offer tunable electronic and steric properties.
Purpose of the Study:
- To synthesize and characterize a novel four-coordinate gold(I)-carbonyl complex.
- To investigate the electronic structure and bonding in gold(I)-carbonyl complexes.
- To compare the properties of gold(I) complexes with their silver(I) and copper(I) analogs.
Main Methods:
- Synthesis of gold(I), silver(I), and copper(I) complexes using tris(pyridyl)borate ligands.
- Isolation and characterization of the complexes via spectroscopic techniques (e.g., IR spectroscopy).
- Computational analysis (e.g., DFT calculations) to probe bonding interactions.
Main Results:
- A unique four-coordinate gold(I)-carbonyl complex with substantial gold-to-CO back-donation was successfully synthesized.
- The C-O stretching frequency in the gold-carbon monoxide complex was notably low, indicating weakened bonding.
- Computational studies revealed significant Au→CO π-back-bonding as a key feature of the Au-CO bond.
Conclusions:
- Tris(pyridyl)borate ligands facilitate the formation of stable gold(I)-carbonyl complexes.
- The observed low C-O stretching frequencies are attributed to strong π-back-bonding from gold to carbon monoxide.
- This work provides insights into the electronic structure of coinage metal carbonyls and the role of back-donation.
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