title: Au(I)...Ag(I) metallophilic interactions between anionic units: theoretical studies on a AuAg4 square pyramidal arrangement.
abstract: We have studied theoretically the organometallic compound (NBu4)2[Au(3,5-C6F3Cl2)2Ag4(CF3CO2)5], whose dianionic part displays a AuAg4 square pyramidal arrangement based on closed-shell Au(I)...Ag(I) interactions between two monoanionic fragments. DFT/B3LYP, ab initio Hartree-Fock (HF), and second-order Møller Plesset perturbation theory (MP2) calculations have been carried out for simplified model systems. Model system [AuPh2]-...[Ag4(CO2H)5]- (C1) has been chosen from DFT results as an appropriate model for the study of the interactions. The four Au(I)...Ag(I) interactions and two additional C...Ag(I) interactions are observed when dispersion-type interactions are considered in the level of theory (MP2) displaying a metallophilic attraction between two anionic units. The study of model C2 (similar to C1 but with minimized C...Ag(I) interactions) permits the study of the Au(I)...Ag(I) interactions separately, which confirms the existence of stabilizing Au(I)...Ag(I) interactions around 13 kJ.mol(-1) each.
authors.affiliation: Departamento de Química, Universidad de La Rioja, Grupo de Síntesis Química de La Rioja, UA-CSIC, Complejo Científico-Tecnológico, 26004-Logroño, Spain. eduardo.fernandez@dq.unirioja.es
authors.forename: Eduardo J
authors.initials: EJ
authors.lastname: Fernández
authors.forename: Antonio
authors.initials: A
authors.lastname: Laguna
authors.forename: José M
authors.initials: JM
authors.lastname: López-de-Luzuriaga
authors.forename: Miguel
authors.initials: M
authors.lastname: Monge
authors.forename: M Elena
authors.initials: ME
authors.lastname: Olmos
authors.forename: Raquel C
authors.initials: RC
authors.lastname: Puelles