Cyclic trinuclear copper(I), silver(I), and gold(I) complexes: a theoretical insight

• Published in: Dalton transactions : an international journal of inorganic chemistry 2015-01, Vol.44 (1), p.377-385
• Main Authors: Caramori, Giovanni F, Piccoli, Rafael M, Segala, Maximiliano, Muñoz-Castro, Alvaro, Guajardo-Maturana, Raul, Andrada, Diego M, Frenking, Gernot
• Format: Article
• Language: English
• Subjects: Anisotropy; Bonding; Boundaries; Conjugation; Covalence; Elevated; Ligands; Mathematical analysis
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/c4dt02514h

The metal-ligand, M-L, bonding situation in cyclic trinuclear complexes, CTCs, of copper(I), silver(I), and gold(I) was investigated in terms of the energy decomposition analysis (EDA-NOCV) and natural bond orbitals (NBOs). The anisotropy of the induced current density (ACID) and magnetic response were employed to evaluate the effect of electronic conjugation and metal-metal interactions in CTCs. The EDA-NOCV results show that the M-L bonding is stronger in gold(I) than in copper(I) or silver(I) complexes. Au(+)-L bonds present an elevated covalent character when compared with Cu(+)-L and Ag(+)-L bonds. The NBO analysis confirms the elevated covalent character observed for Au(+)-L bonds, indicating that the ligand-metal donation, L → M, and the metal-ligand back-donation, M → L, are more stabilizing in gold(I) than in copper(I) or silver(I) complexes. Both ACID and the magnetic response calculations reveal that there are cyclic conjugations in the ligands and a strong diatropic ring current indicating the presence of aromaticity. However, there is no through-bond M-L conjugation between the ligands and the metallic centers, as indicated by the absence of a continuous anisotropy boundary surface involving M-L bonds.