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On the structure of Zn(II) and Cu(II) cyanin complexes in aqueous solution

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Abstract

B3LYP/6-31++G(d,p) optimizations on models for the metal cyanin, Cy, complexes [MCy(H2O) n ]+, (M = Zn(II), Cu(II); n = 2, 3, 4) in aqueous solution indicate that 4 is the most favoured coordination number in both cases. SP -4 and T -4 geometries are nearly isoenergetic for the former, while SP -4 is the only one obtained for the latter. Anionic cyanin displays higher affinity for Cu(II) than for Zn(II) or Mg(II). The electron density reorganization of cyanin model accompanying the complexation process was analyzed by means of the quantum theory of atoms in molecules. This analysis reveals that: (1) the O4′–M bond is stronger than O3′–M; (2) anionic cyanin displays a dual character between 4′-keto-quinoidal and 3′,4′-dienolate resonance forms; (3) Cu(II) takes more electron density than Zn(II) from Cy− and water ligands; (4) when the coordination number increases, each ligand (Cy− or water) transfers less electron density; (5) complex formation modifies the electron density in all the atoms of the ligands, but the largest modifications are displayed within the AC bicycle of Cy−; and (6) a third part of density lost by the Cy− ligand is removed from hydrogens.

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Acknowledgments

The authors thank “Centro de Supercomputación de Galicia” (CESGA) for free access to its computational facilities, and financial support from Spanish Ministry of Economy through research project CTQ2010-21500.

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Authors and Affiliations

  1. Departamento de Química Inorgánica, Universidade de Vigo, Lagoas-Marcosende s/n, 36310, Vigo, Galicia, Spain

    Mercedes García Bugarín

  2. Departamento de Química Física, Facultade de Química, Universidade de Vigo, Lagoas-Marcosende s/n, 36310, Vigo, Galicia, Spain

    Ricardo A. Mosquera

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  1. Mercedes García Bugarín
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  2. Ricardo A. Mosquera
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Correspondence to Ricardo A. Mosquera.

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11224_2014_445_MOESM1_ESM.doc

Supplementary material 1 (DOC 388 kb): Absolute values for atomic electron populations in the model of anionic cyanin and their variations upon complexation in the diverse cases here considered are available as Supporting Information

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García Bugarín, M., Mosquera, R.A. On the structure of Zn(II) and Cu(II) cyanin complexes in aqueous solution. Struct Chem 25, 1647–1657 (2014). https://doi.org/10.1007/s11224-014-0445-z

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  • DOI: https://doi.org/10.1007/s11224-014-0445-z

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