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Coordination complexes of 4-methylimidazole with ZnII and CuII in gas phase and in water: a DFT study

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Abstract

A quantum chemistry study of mononuclear metal coordination with four 4-methylimidazole ligands (4-MeIm) was investigated. The four complexes [Cu(4-MeIm)4]2+, [Cu(4-MeIm)4, H2O]2+, [Zn(4-MeIm)4]2+ and [Zn(4-MeIm)4, H2O]2+ were studied with particular attention to the Nπ or Nτ possible coordinations of the 4-MeIm ring with the metals, using different DFT methods. The results suggest that the Nτ coordination of 4-MeIm ring to ZnII or CuII is more favorable whatever the level of calculation. In contrast, the addition of one water molecule in the first coordination sphere of the metal ions provides five-coordinated complexes showing no Nπ or Nτ preferences. There is good agreement between the DFT-calculated structure and those available experimentally. When metal ions are four-fold coordinated, they adopt a tetrahedral geometry. When CuII and ZnII are five-fold coordinated, highly symmetric structures or intermediate structures are calculated. Similar energies are calculated for different structures, suggesting flat potential energy surfaces. The addition of implicit solvent modifies the calculated first coordination sphere, especially for [Cu(4-MeIm)4, H2O]2+ structures. The QTAIM and ELF topological analyses of the interaction between CuII and the neutral ligands, clearly indicate a dative bonding with a strong ionic character.

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Acknowledgments

Calculations (projects x2015087394 and x2016087394) were carried out on the IBM SP4 computers of the CINES (Centre Informatique National de l’Enseignement Supérieur) in Montpellier (France) and of the IDRIS (Institut des Ressources en Informatique Scientifique) in Orsay (France). MB is grateful to MESRS (Ministère de l’Enseignement Supérieur et de la Recherche Scientifique), Tunisia for an 11-month grant.

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Authors and Affiliations

  1. Departement de Physique Laboratoire de Physique de la Matière Condensée (LPMC) Faculté des Sciences de Tunis, Université de Tunis El Manar, Campus Universitaire 2092, Tunis, Tunisia

    Malek Boukallaba & Boutheïna Kerkeni

  2. Institut Charles Gerhardt, MACS, UMR 5253 CNRS-ENSCM-UM, 8 rue de l’Ecole Normale, 34296, Montpellier Cedex 5, France

    Malek Boukallaba & Dorothée Berthomieu

  3. Université de la Manouba, Institut Supérieur des Arts Multimédia de la Manouba, 2010, la Manouba, Tunisia

    Boutheïna Kerkeni

  4. CNRS, LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, BP 44099, 31077, Toulouse Cedex 4, France

    Christine Lepetit

  5. Université de Toulouse, UPS, INPT, 31077, Toulouse Cedex 4, France

    Christine Lepetit

  6. LPCNO, UMR 5215 CNRS-INSA-UPS, 135 avenue de Rangueil, 31077, Toulouse Cedex 4, France

    Dorothée Berthomieu

Authors
  1. Malek Boukallaba
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  2. Boutheïna Kerkeni
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  3. Christine Lepetit
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  4. Dorothée Berthomieu
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Correspondence to Dorothée Berthomieu.

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This paper belongs to Topical Collection Festschrift in Honor of Henry Chermette.

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Boukallaba, M., Kerkeni, B., Lepetit, C. et al. Coordination complexes of 4-methylimidazole with ZnII and CuII in gas phase and in water: a DFT study. J Mol Model 22, 301 (2016). https://doi.org/10.1007/s00894-016-3167-x

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  • DOI: https://doi.org/10.1007/s00894-016-3167-x

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