We have studied theoretically the organometallic compound [{Au(C6Cl5)2}Ag([9]aneS3)]2, which displays an unprecedented [Ag]+–[Au]–[Au]–[Ag]+ sequence of metals, formed by unsupported Au(I)...Au(I) and Au(I)...Ag(I) interactions and weaker Cipso ...Ag and C6Cl5...C6Cl5 p-stacking interactions. Density Functional Theory calculations using the pbe functional (DFT/pbe), Hartree–Fock (HF), and second-order Møller Plesset perturbation theory (MP2) calculations have been performed on five model systems based on the X-ray structure. Two dinuclear models (A1 and A2) have been used to estimate the BSSE-corrected interaction energy at HF and MP2 levels between one Ag(I) and one Au(I) fragment and permit to separate the Cipso...Ag(I) and Au(I)...Ag(I) contribution to the interaction. Three tetranuclear models (B1–B3) have been used to determine the Cipso ...Ag(I), Au(I)...Ag(I), Au(I)...Au(I) and p-stacking interactions present in the molecule. The HF level accounts for the ionic component of the interactions and the MP2 level also account for the dispersive contribution; both permits to study the nature and strength of all different types of interactions present in the molecule.
Theoretical studies on an unusual [Ag]+...[Au]-...[Au]-...[Ag]+metallophilic pattern: Dispersive forces vs. classical coulomb forces
LIPPOLIS, VITO
2014-01-01
Abstract
We have studied theoretically the organometallic compound [{Au(C6Cl5)2}Ag([9]aneS3)]2, which displays an unprecedented [Ag]+–[Au]–[Au]–[Ag]+ sequence of metals, formed by unsupported Au(I)...Au(I) and Au(I)...Ag(I) interactions and weaker Cipso ...Ag and C6Cl5...C6Cl5 p-stacking interactions. Density Functional Theory calculations using the pbe functional (DFT/pbe), Hartree–Fock (HF), and second-order Møller Plesset perturbation theory (MP2) calculations have been performed on five model systems based on the X-ray structure. Two dinuclear models (A1 and A2) have been used to estimate the BSSE-corrected interaction energy at HF and MP2 levels between one Ag(I) and one Au(I) fragment and permit to separate the Cipso...Ag(I) and Au(I)...Ag(I) contribution to the interaction. Three tetranuclear models (B1–B3) have been used to determine the Cipso ...Ag(I), Au(I)...Ag(I), Au(I)...Au(I) and p-stacking interactions present in the molecule. The HF level accounts for the ionic component of the interactions and the MP2 level also account for the dispersive contribution; both permits to study the nature and strength of all different types of interactions present in the molecule.
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