Understanding the bonding and aromaticity of [Au{CH(X)E}] (X = CF, CN, BO; E = Si, Ge): trinuclear gold superhalogens

• Published in: New journal of chemistry Vol. 48; no. 11; pp. 4765 - 4771
• Main Authors: Das, Subhra, Sinha, Swapan, Roymahapatra, Gourisankar, Orozco-Ic, Mesas, Chandra De, Gobinda, Giri, Santanab
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 11.03.2024
• Subjects: Aromaticity; Bonding; Critical point; Density functional theory; Electron density; Gold; Halogens; Mathematical analysis; Stability
• ISSN: 1144-0546; 1369-9261
• DOI: 10.1039/d3nj05422e

Carbene and its analogous silylene and germylene ligated trinuclear gold complexes are well established due to their cationic stability, but the anionic stability of such complexes is still rare. Density functional theory calculations on recently synthesized [Au 3 {C 4 H 4 (SiMe 3 ) 4 Si} 3 ] and [Au 3 {C 4 H 4 (SiMe 3 ) 4 Ge} 3 ] prove that the Au 3 core is electron rich and the calculated vertical detachment energy is close to that of halogens. Further proper ligand manipulation on these complexes makes them remarkably stable anions having electron binding energies higher than 5 eV and behaving like superhalogens. Magnetic response calculations based on the magnetically induced current densities and the induced magnetic field confirm the aromatic nature of these anionic Au 3 -complexes. A study of the gradient Laplacian of electron density and energy density at the bond critical point and electron localization function gives additional bonding information of these anionic complexes. The first Principal study on [Au 3 {C 4 H 4 (X) 4 E} 3 ] (X = CF 3 , CN, BO; E = Si, Ge) reveals their superhalogen character with anionic trinuclear Au 3 core. Magnetic response calculations based on the magnetically induced current densities and the induced magnetic field confirm the aromatic nature.