Chelating properties of EDTA-type ligands containing six-membered backbone ring toward copper ion: Structure, EPR and TD-DFT evaluation
| Autor: | Robert J. Deeth, Marina Cendic, Daniele Sanna, Auke Meetsma, Eugenio Garribba, Zoran D. Matović |
|---|---|
| Přispěvatelé: | Solid State Materials for Electronics |
| Jazyk: | angličtina |
| Rok vydání: | 2017 |
| Předmět: |
ENERGIES
chemistry.chemical_element Protonation Crystal structure 010402 general chemistry 01 natural sciences law.invention Inorganic Chemistry DENSITY-FUNCTIONAL THEORY IMPURITY Computational chemistry law Syntheses LFMM Materials Chemistry SPECTRA Chelation CRYSTAL-STRUCTURE Physical and Theoretical Chemistry Electron paramagnetic resonance STEREOCHEMISTRY GEOMETRICAL-ISOMERS COPPER(II)-EDTA-TYPE COMPLEXES 010405 organic chemistry Copper(II)-aminopolycarboxylates RESONANCE Copper 0104 chemical sciences ELECTRONIC-PROPERTIES Crystallography chemistry Octahedron Density functional theory EPR TD-DFT Cis–trans isomerism |
| Zdroj: | Polyhedron, 124, 215-228. PERGAMON-ELSEVIER SCIENCE LTD Polyhedron 124 (2017): 215–228. doi:10.1016/j.poly.2016.12.025 info:cnr-pdr/source/autori:Cendic, Marina; Deeth, Robert J.; Meetsma, Auke; Garribba, Eugenio; Sanna, Daniele; Matovic, Zoran D./titolo:Chelating properties of EDTA-type ligands containing six-membered backbone ring toward copper ion: Structure, EPR and TD-DFT evaluation/doi:10.1016%2Fj.poly.2016.12.025/rivista:Polyhedron/anno:2017/pagina_da:215/pagina_a:228/intervallo_pagine:215–228/volume:124 |
| ISSN: | 0277-5387 |
| DOI: | 10.1016/j.poly.2016.12.025 |
| Popis: | The P-APC ligands (EDTA-like aminopolycarboxylate ligands comprising 1,3-propanediamine backbone) H(4)pdta, H(4)pd(3)ap, H(4)pddadp and H(4)pdtp (H(4)pdta = 1,3-propanediamine-N,N,N',N'-tetraacetatic acid; H(4)pd(3)ap = 1,3-propanediamine-N,N,N'-triacetic-N'-3-propionic acid; H4pddadp = 1,3-propanediamine-N,N'-diacetatic-N,N'-di-3-propionic acid; H(4)pdtp = 1,3-propanediaminetetra-3-propionic acid) were investigated. The chelating ligands coordinate to copper(II) via five or six donor atoms affording distorted trigonal-bipyramid and octahedral structures that were verified by X-ray analysis for Ba[Cu(pd(3)ap)]center dot 6H(2)O (1) and trans(O-6)-Ba[Cu(pddadp)]center dot 8H(2)O (2) complexes respectively. The impact of counter-ions on the P-APC complexes is shown in detail together with the analysis of another strain parameters. EPR spectral results confirm the penta-coordination of 1 and hexa-coordination of 2 in aqueous solution, even if several Cu(II) species with different protonation degree exist as a function of pH, and indicate that a hexa-coordinated structure is favored when the two axial COO- donors close five-membered chelate rings. We also present here the results of molecular mechanics (LFMM) calculations based on our previously-developed force field along with results of DFT (Density Functional Theory). On the basis of extensive DFT and TD-DFT calculations the B1LYP/6-311++G(d,p) level has been seen as an accurate theory for calculating and predicting the UVVis spectra in case of copperP-APC compounds. (C) 2016 Elsevier Ltd. All rights reserved. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Full Text from ScienceDirect