DIMERIZATION OF MALEINATE CHLOROCOMPLEXES OF Cu+. QUANTUM-CHEMICAL MODELING
DOI:
https://doi.org/10.15421/jchemtech.v33i3.333798Keywords:
maleate aquachlorocomplexes, Cu , dimerization, quantum chemical modelingAbstract
The article presents the results of a theoretical study of the dimerization processes of Cu+ maleate complexes in an aqueous medium in the presence of chlorine anions. Quantum-chemical modeling by the DFT method (Gaussian 09, AIM2000) showed that the synthesis of Cu+ maleate π-complexes using CuCl salt as a precursor can be accompanied by dimerization of the product. Moreover, in addition to [L-Cu2Cl2-L] dimers, [H2O-Cu2Cl2-H2O] dimers can also be formed in solution. Consideration of the probable reactions of the interaction of maleic acid with dimeric aquachloro complexes allowed us to establish that the dimeric core cannot simultaneously contain both water and maleic acid in its internal coordination sphere. Comparison of the energy parameters of various reactions involving the [Cu2Cl2] cluster, water molecules, and all forms of maleic acid indicates that the most energetically favorable structures are dimers of anionic complexes. Therefore, in a weakly acidic environment, one should expect the appearance of [HM-Cu2Cl2-HM]2– ions, and in neutral and alkaline environments, [M-Cu2Cl2-M]4– ions. It has been established that the addition of all forms of maleic acid to [Cu2Cl2] leads to the rupture of the Cu-Cu bond and, as a consequence, to the weakening of this core in [L-Cu2Cl2-L] dimers.
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