Estudo teórico QTAIM e DFT dos compostos de coordenação: efeito quelato, titanocenos e ligação química

This work is a study of coordination compounds by quantum theory of atoms in molecules (QTAIM), based on the topological analysis of the electron density of molecular systems, both theoretically and experimentally obtained. The coordination chemistry topics which were studied are the chelate effect, bent titanocene and chemical bond in coordination complexes. The chelate effect was investigated according to topological and thermodynamic parameters. The exchange of monodentate ligands on polydentate ligands from same transition metal increases the stability of the complex both from entropy and enthalpy contributions. In some cases, the latter had a higher contribution to the stability of the complex in comparison with entropy. This enthalpic contribution is explained according to topological analysis of the M-ligand bonds where polidentate complex had higher values of electron density of bond critical point, Laplacian of electron density of bond critical point and delocalization index (number of shared electrons between two atoms). In the second chapter, was studied bent titanocenes with bulky cyclopentadienyl derivative π-ligand. The topological study showed the presence of secondary interactions between the atoms of π-ligands or between atoms of π-ligand and -ligand. It was found that, in the case of titanocenes with small difference in point group symmetry and with bulky ligands, there was an nearly linear relationship between stability and delocalization index involving the ring carbon atoms (Cp) and the titanium. However, the titanocene stability is not only related to the interaction between Ti and C atoms of Cp ring, but secondary interactions also play important role on the stability of voluminous titanocenes. The third chapter deals with the chemical bond in coordination compounds by means of QTAIM. The quantum theory of atoms in molecules so far classifies bonds and chemical interactions in two categories: closed shell interaction (ionic bond, hydrogen bond, van der Waals interaction, etc) and shared interaction (covalent bond). Based on topological parameters such as electron density, Laplacian of electron density, delocalization index, among others, was classified the chemical bond in coordination compounds as an intermediate between closed shell and shared interactions

Síntese e caracterização de compostos de coordenação homolépticos e heterolépticos com o ligante ácido kójico

The present work has as main objective to contribute to the coordination chemistry of the ligand kojic acid, with the synthesis and characterization of the homoleptic compounds [Al(kj)3], [Fe(kj)3], [Fe(kj)2], [Cu(kj)2] e [Ru(kj)3], and the new heteroleptic complexes, trans- K2[Fe(kj)2(CN)2] and trans-Na2[Ru(kj)2(CN)2]. The obtained compounds were characterized by vibrational spectroscopy in the infrared region (IV) and Electronic spectroscopy in the ultraviolet and visible region (Uv-Vis). The infrared results indicated the coordination of the bidentate ligand kojic acid, due to reductions in the values of the stretching frequencies of the carbonyl and double bonds, compared to the free ligand for all complexes obtained. The presence of new vibrational modes indicated the change of symmetry of the molecules in the new compounds synthesized. Additionally, the presence of vibrational modes assigned to metal-oxygen also contributed to confirm the ligand coordinating to the metal ions. Through this technique, was also possible to perform correlations of the numbers of vibrational modes, in the region 1400-900 cm-1 and the compounds geometry. The heteroleptic compounds exhibited υC≡N in 2065 and 2053 cm-1, respectively, for the trans-K2[Fe(kj)2(CN)2] and trans-Na2[Ru(kj)2(CN)2], indicating coordination of the cyano ligand to metal ions FeII e RuII. Comparing the obtained values with literature data was possible to identify the complex isomerism as trans. In relation to the results of electronic spectroscopy, studies of pH variation of kojic acid provided information on the distribution of electron density in the molecule, showing characteristic spectral profile of kojic ion and its protonated form (Hkj, kojic acid), with two bands at 215 and 269 nm, or deprotonated (kj-), with bands at 226 and 315 nm. The electronic spectra obtained for all complexes in aqueous medium, in the ultraviolet region, exhibited variations of the energies assigned to kojic acid intraligand transitions while in the visible region, only transitions assigned to charge transfer of iron and ruthenium complex have been identified

Síntese e caracterização de complexo tetranuclear de cobre com o ligante resorcinareno

The main objective of the present work is to contribute to the development of the coordination chemistry of macromolecules such as resorcinarene with the synthesis and characterization of new copper complexes with chloride, vanillin and resorcinarene binders, all coordinated to phenanthroline, a biologically active molecule with important properties in biological systems. The complex [(Cu(phen))4(resvan)], was synthesized from the direct reaction of the metals with resorcinarene and generates several possibilities for coordination, which hinders its characterization. Therefore, in order to limit the coordination sites of the ligand, the complex [(Cu(phen))4(resvan)]Cl4 was formed from a new synthetic methodology. The complex cis-[Cu(phen)Cl2], cis-[Cu(phen)(van)]Cl, [(Cu(phen))4(resvan)] and [(Cu(phen))4(resvan)]Cl4 were characterized by spectroscopic techniques such as IR, UV-vis and EPR. By using infrared it has been possible to demonstrate the presence of the phenanthroline ligand in the synthesized complexes, and vanillin in the complex cis- [Cu(phen)(van)]Cl and resvan ligand in the complex [(Cu(phen))4(resvan)], besides this indicating the formation of resorcinarene in the complex [(Cu(phen))4(resvan)]Cl4. The electronic spectra of these coordination compounds indicated the presence of the phenanthroline ligand, by its intense bands in the ultraviolet region. For the complex cis- [Cu(phen)(van)]Cl it still indicated the presence of the ligand vanillin based on intraligand bands of vanillin and charge transfer, LMCT. Furthermore, the spectra showed d-d bands, confirming the formation of metal compounds. The amount of copper atoms present in the complex [(Cu(phen))4(resvan)]Cl4 was estimated from a comparative analysis of the absorbances of solutions of the same concentration of [(Cu(phen))4(resvan)]Cl4 and cis- [Cu(phen)(van)]Cl, which indicates that these compounds have copper atoms in the ratio 4:1. The EPR spectra of the complex cis-[Cu(phen)Cl2], cis-[Cu(phen)(van)]Cl and [(Cu(phen))4(resvan)]Cl4 showed axial profiles, while the complex [(Cu(phen))4(resvan)] showed of axial and rhombic profiles, indicating a change in the symmetry of the Cu (II) to this complex environment. The binders vanillin and resvan underwent biological assays with satisfactory results, both exhibited antioxidant activity and low toxicity, as well vanillin present antitoxoplásmico character.