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Bonding and electronic structures in dinuclear (X)[(Ind)M2L2] complexes (M = Ni, Pd, L = CO, PEt3, X = Cl, Allyl, Ind = indenyl, Cp = cyclopentadienyl): analogy between four-electron donor ligands

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Abstract

The calculations of bimetallic complexes of the type (X)[(Ind)M2(L)2] (M = Ni, Pd, L = CO, (PEt3) and X = Allyl, Cp and indenyl) have been done using two DFT functionals, namely BP86 and B3LYP*. The allyl, Cp and indenyl ligands adopt the same η3-coordination mode with a π bond and can be considered to be isolobal, while the chloride acts as σ- and π-donor. The computed structural and energetic parameters and energy decomposition yield chemically useful information. We report that the metal–metal bond distances are slightly sensitive to the electron donation and electron π-backdonation as the isolobal prediction suggests. Changing the metal from Ni to Pd has the result of increasing the metal–metal bond distance, decreasing the natural population of Pd and the weakness interactions between the X− ligand and the [(Ind)M2(L)2]+ fragment. The results showed that the four ligands behave quite similarly in terms of bonding, coordination mode and donation and π-backdonation properties highlighted by the orbitals’ populations and the energy decomposition. However, the strength of interactions can be classified as follows: Cl < Cp ≈ Ind < Allyl. In all the complexes studied, the M22+ moiety adopts a single metal–metal bonding attributing the 16-MVE configuration to each M(I) cation.

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Acknowledgements

The authors acknowledge 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) for financial support.

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  1. Laboratoire de Chimie appliquée et Technologie des Matériaux, Université Larbi Ben M’Hidi - Oum el Bouaghi, 04000, Oum el Bouaghi, Algeria

    Sabri Mecheri, Bachir Zouchoune & Saber-Mustapha Zendaoui

  2. Unité de Recherche de Chimie de l’Environnement et Moléculaire Structurale, Université Constantine (Mentouri), 25000, Constantine, Algeria

    Bachir Zouchoune & Saber-Mustapha Zendaoui

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This work is dedicated to Doctor Jean-François Halet on the occasion of his 60th birthday.

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Mecheri, S., Zouchoune, B. & Zendaoui, SM. Bonding and electronic structures in dinuclear (X)[(Ind)M2L2] complexes (M = Ni, Pd, L = CO, PEt3, X = Cl, Allyl, Ind = indenyl, Cp = cyclopentadienyl): analogy between four-electron donor ligands. Theor Chem Acc 139, 12 (2020). https://doi.org/10.1007/s00214-019-2526-y

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