RESUMEN
In this paper, metallocene-fullerene hybrid complexes, [M(η5 -Cp)(η5 -C60 Me5 )] (M = Fe2+ , Ru2+ , Os2+ ), as well as corresponding classical metallocenes have been studied theoretically at BP86/def2-SVP and M06L/def2-SVP levels of theory. With considering these metal complexes as an ABA' system (B is the central metal ion and A and A' are related η5 -ligands), the total interaction energies were calculated using common methods, as well as by calculating the interaction energies between the four defined pairs of fragments including A-B, B-A', A-BA', and AB-A'. The resulting data clearly showed that in all complexes there is a strong anticoopertivity between two metal-(η5 -ligand) bonds. In order to understand the origin of difference in values of various calculated interactions in above two types of complexes, the nature of metal-ligand bonds was also studied using energy decomposition analysis-natural orbital for chemical valence calculations. The results showed that in hybrid complexes, in contrast to metallocenes, the orbital interactions are considerably larger than electrostatic interactions.
RESUMEN
In this work we have attempted to computationally analyze the important parameters affecting the selectivity in host-guest systems in order to show that the solvent effect in some host-guest systems is even more important than the hole-size fitting and/or host-guest interaction energy. For this purpose, the fluoride anion selectivities of the five most studied azacryptands with different affinities, moieties, cavity sizes and degrees of preorganization, in their fully protonated forms, were studied at PBE/TZVP and B3P86/TZVP levels of theory. The factors affecting the selectivity such as hole size fitting, steric effects, electronic properties, preorganization of hosts, as well as solvent effects were investigated. The results showed that among the five studied azacryptands, one of them, which ranks fifth for selectivity according to its weak interaction energy with fluoride anions, ranks fourth due to its good preorganization. However, a surprising improvement occurs when its selectivity for fluoride anions ranks first due to the existence of less solvent hindrance. The results of the calculations were further confirmed by a good correlation between the calculated and experimental formation constants.
RESUMEN
The reaction of K2[PdCl4] and PdCl2 with 5-methyl-5-(4-pyridyl)-2,4-imidazolidenedione (L) proceeded with the formation of two different Pd complexes, PdL2Cl2 (1) and PdL2Cl4 (2c), corresponded to a substitution reaction and a substitution reaction along with unanticipated oxidation, respectively. The nature of the oxidizing agent is unknown. These compounds have been studied by elemental analysis, IR, (1)H and (13)CNMR, molar conductivity, and cyclic voltammetry. In addition, structural optimization by DFT calculations and simulation of NMR spectra have been performed and compared with the experimental data. NBO analysis, HOMO and LUMO, have been used to elucidate the information regarding charge transfer within the molecules. Theoretical studies confirmed that in 1 and 2c the trans structures are about 41 and 33 kJ mol(-1) more stable than cis ones. Antibacterial activity and in vitro cytotoxicity of these compounds, as respectively assessed in six bacterial strains and two human tumor cell lines, have been investigated. Results showed the title complexes have the capacity of inhibiting the metabolic growth of bacteria and tumor cells to different extents.