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Cyclic trinuclear copper(I), silver(I), and gold(I) complexes: a theoretical insight.
Giovanni F Caramori1, Rafael M Piccoli, Maximiliano Segala
1Departamento de Química, Universidade Federal de Santa Catarina, CP 476, Florianópolis, SC 88040-900, Brazil. giovanni.caramori@ufsc.br.
Gold complexes exhibit stronger metal-ligand bonds with greater covalent character compared to copper and silver cyclic trinuclear complexes (CTCs). Aromaticity is present in the ligands, but not through the metal-ligand bonds.
Area of Science:
- Inorganic Chemistry
- Computational Chemistry
- Materials Science
Background:
- Cyclic trinuclear complexes (CTCs) are crucial in coordination chemistry.
- Understanding metal-ligand (M-L) bonding is key to designing new materials.
- Copper(I), silver(I), and gold(I) complexes offer diverse electronic properties.
Purpose of the Study:
- Investigate the M-L bonding in CTCs of Cu(I), Ag(I), and Au(I).
- Evaluate electronic conjugation and metal-metal interactions within these complexes.
- Determine the presence and nature of aromaticity in the CTCs.
Main Methods:
- Energy Decomposition Analysis with Natural Orbitals for Chemical Valence (EDA-NOCV).
- Natural Bond Orbital (NBO) analysis.
- Anisotropy of the Induced Current Density (ACID) and magnetic response calculations.
Main Results:
- M-L bonding is strongest in gold(I) complexes, showing increased covalent character.
- NBO analysis confirms enhanced ligand-to-metal donation and metal-to-ligand back-donation in gold(I) complexes.
- ACID and magnetic response indicate ligand aromaticity via cyclic conjugation and diatropic ring currents, but no through-bond M-L conjugation.
Conclusions:
- Gold(I) complexes display superior M-L bonding stability and covalency compared to copper(I) and silver(I) counterparts.
- The ligands in these CTCs exhibit aromatic character.
- Absence of through-bond conjugation suggests limited electronic communication between metal centers through the ligands.
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