DFT analysis of the interaction between Hg and monodentate neutral ligands using NBO, EDA, and QTAIM.

We report thermodynamic, geometric, and electronic parameters for the interaction between neutral ligands and the [Hg(HO)] dication, using the B3LYP/6-311 + G(d,p) approach. Gibbs free energies for the interaction were employed to rank the affinity order of the several neutral ligands. To identify the parameters that characterize the affinity between the two fragments, the metal-ligand interaction was analyzed according to the EDA, NBO, and QTAIM decomposition schemes.

Evaluation of 5-hydroxy-1,4-naphthoquinone-cobalt(III) complexes for hypoxia-activated drug delivery.

Three novel PyNcobalt(III) complexes with the 5-hydroxy-1,4-naphthoquinone nuclei (NQ) were evaluated as potential hypoxia-activated anticancer prodrugs. The complexes were synthesized and fully characterized by IR and UV-Visible spectroscopies, ESI mass spectrometry and CHN elemental analysis. Structural information was obtained from density functional theory (DFT) calculations.

A DFT study of the interaction between [Cd(HO)] and monodentate O-, N-, and S-donor ligands: bond interaction analysis.

A series of B3LYP/6-311+G(d,p) calculations of the affinity of monodentate ligands for [Cd(HO)] are performed. Three types of ligands containing O (phosphine oxide, lactam, amide, carboxylic acid, ester, ketone, aldehyde, ether, halohydrin, enol, furan), N (thiocyanate, amine, ammonia, azide), and S (thioester, thioketone, thiol, thiophene, disulfide) interacting atoms are investigated. The results show that phosphine oxide has the largest affinity for the cadmium cation due to the polarization of the P=O bond.

A density functional theory investigation of the interaction of the tetraaqua calcium cation with bidentate carbonyl ligands.

Calcium complexes with bidentate carbonyl ligands are important in biological systems, medicine and industry, where the concentration of Ca is controlled using chelating ligands. The exchange of two water molecules of [Ca(HO)] for one bidentate monosubstituted and homo disubstituted dicarbonyl ligand was investigated using the B3LYP/6-311++G(d,p) method. The ligand substituents NH, OCH, OH, CH, H, F, Cl, CN and NO are functional groups with distinct electron-donating and -withdrawing effects that bond directly to the sp C atom of the carbonyl group.

DFT studies of imino and thiocarbonyl ligands with the pentaaqua Mg²⁺ cation: affinity and associated parameters.

The affinity of the pentaaqua Mg(2+) cation for a set of para-substituted imino [HN = CHC₆H₄(R)] and thiocarbonyl [S = CHC₆H₄(R)] ligands (R = H, F, Cl, Br, OH, OCH₃, CH₃, CN, NH₂ and NO₂) was analyzed with DFT (B3LYP/6-31+G(d)) and semi-empirical (PM6-DH2) methods. The interaction enthalpy was calculated to quantify the affinity of the Mg(2+) cation for the ligands. Additionally, geometric and electronic parameters were correlated with the intensity of the metal-ligand interaction.

Vibrational spectra of tris(dmit) complexes of main group metals: infrared, Raman and ab initio calculations.

Infrared Fourier Transform investigation of several metal tris-complexes of 1,3-dithiole-2-thione-4,5-dithiolate (dmit) ligand have been recorded within a theoretical-experimental investigation of the vibrational molecular spectra of crystalline [NEt4]2[Sn(dmit)3] and [NEt4][Sb(dmit)3] compounds. For the [Sn(dmit)3]-2 anion we recorded as well the Raman Fourier Transform spectra. Ab initio calculations have been carried with several ECPs, basis sets and methodologies (RHF and DFT) in order to assess family and methodological errors precisely.