Gas phase and solution state stability of complexes L…M, where M = Cu, Ni, or Zn and L = R−C(O)NHOH (R = H, NH2, CH3, CF3, or Phenyl) |
| |
Authors: | Július ille Martin ramko Vladimír Garaj Milan Remko |
| |
Institution: | aDepartment of Pharmaceutical Chemistry, Faculty of Pharmacy, Comenius University, Odbojarov 10, SK-832 32 Bratislava, Slovakia |
| |
Abstract: | The structure and gas-phase metal affinities (M = Cu2+, Ni2+, and Zn2+) of formohydroxamic acid derivatives R–C(O)NHOH (R = H, NH2, CH3, CF3 and Phenyl) were studied using the B3LYP/6-311+G(d,p) method of DFT theory. In order to evaluate the conformational behavior of these systems in water, we carried out CPCM-SCRF optimization calculations at the B3LYP/6-311+G(d,p) levels of theory. The obtained optimized geometries and interaction affinities of the gas and solution phase were compared. The following order of stability was found for ionic complexes of the transition metals: Cu2+ > Ni(t)2+ > Zn2+. The same stability order would be expected according to the Irving–Williams order of stability constants. The high-spin complexes of the Ni2+ were more stable than the low-spin complexes. The solvent effect reduced the observed relative stability of individual metallic complexes of substituted hydroxamic acids. |
| |
Keywords: | Substituted hydroxamic acids Cu2+ Ni2+ and Zn2+ complexes DFT Interaction enthalpy and Gibbs energy Solvent effect |
本文献已被 ScienceDirect 等数据库收录! |
|