Structural Chemistry

, Volume 30, Issue 5, pp 1859–1871 | Cite as

DFT investigation of homotrinuclear and heterotrinuclear [M3(Phz)2], [MM′2(Phz)2], [M3(CO)2(Phz)2], [MM′2(CO)2(Phz)2] sandwich complexes (M = Ti, Cr, Fe and Ni; M′ = V and Mn, Phz = C12H8N2): predicted models and electronic structures

  • Bachir ZouchouneEmail author
  • Meriem Merzoug
  • Narimene Bensalem
Original Research


The results described in this work report a DFT/BP86 (using the TZ2P basis) study concerning the molecular and electronic structures of homotrinuclear and heterotrinuclear substituted and unsubstituted complexes. It is about the interaction between a trimetallic M3 moiety flanked between two phenazine (Phz) ligand which is a 14-π electron donor ligand. Each of the six-membered rings of each phenazine tends to establish M-L bonding with various hapticies from η2 to η6 according to the electron need and the nature of the metal. The most stable [Ti3(Phz)2] and [Cr3(Phz)2] complexes have a comparable closed-shell electronic configuration of 18-/18-/18-MVE with the same η666 coordination mode. However, the [Cr3(Phz)2] and [Ni3(Phz)2] complexes correspond to 17-/18-/17 and 14-/14-/14-MVE electronic configurations, respectively. The unsubstituted heterotrinuclear [Cr(V)2(Phz)2] and [Cr(Mn)2(Phz)2] complexes are the most stable in the models wherein the highest electronegative atoms are adjacent, contrary to the [Ti(V)2(Phz)2] species which are favored in the case where the identical Ti atoms are separated by the vanadium one. All unsubstituted complexes display M-M bonding, conversely to the carbonyl-substituted complexes which prefer the M-CO bonding rather than the M-M ones. The triple, double, and single M-M bonding present in the proposed models are identified by the bond distances, Wiberg index, and MO plots according to the valence electron count of the M3 moiety.


Coordination modes Metal-ligand interactions Natural bond analysis Spin contamination 


Authors’ contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.


The authors received financial support from the Algerian MESRS (Ministère de l’Enseignement Supérieur et de la Recherche Scientifique) and DGRSDT (Direction Générale de la Recherche Scientifique et du Développement Technologique).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interest.

Supplementary material

11224_2019_1322_MOESM1_ESM.docx (38 kb)
ESM 1 Table S1-S7: Selected calculated parameters for [M3(Phz)2], [M3(CO)2(Phz)2], [MM′2(Phz)2] and [MM′2(CO)2(Phz)2] (M = Ti, Cr, Fe and Ni; M′ = V and Mn) complexes. The bond distances are given in (Å), the HOMO-LUMO gaps are given in (eV) and the relative energies between isomers are given in (kcal/mol). (DOCX 37 kb)


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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Bachir Zouchoune
    • 1
    • 2
    Email author
  • Meriem Merzoug
    • 1
  • Narimene Bensalem
    • 1
  1. 1.Laboratoire de Chimie appliquée et Technologie des MatériauxUniversité Larbi Ben M’Hidi-Oum El BouaghiOum El BouaghiAlgeria
  2. 2.Unite de Recherche de Chimie de l’Environnement et Moleculaire StructuraleUniversité-Constantine (Mentouri)ConstantineAlgeria

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