TY - JOUR
T1 - Cyclic trinuclear copper(i), silver(i), and gold(i) complexes
T2 - A theoretical insight
AU - Caramori, Giovanni F.
AU - Piccoli, Rafael M.
AU - Segala, Maximiliano
AU - Muñoz-Castro, Alvaro
AU - Guajardo-Maturana, Raul
AU - Andrada, Diego M.
AU - Frenking, Gernot
N1 - Publisher Copyright:
© The Royal Society of Chemistry 2015.
PY - 2015/1/7
Y1 - 2015/1/7
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84915747105&partnerID=8YFLogxK
U2 - 10.1039/c4dt02514h
DO - 10.1039/c4dt02514h
M3 - 文章
AN - SCOPUS:84915747105
SN - 1477-9226
VL - 44
SP - 377
EP - 385
JO - Dalton Transactions
JF - Dalton Transactions
IS - 1
ER -