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Coordination and ligands’ effects in trinuclear [Pd3(COT)2(L)]2+ (L = H2O, CO, N2, HCN, HNC, NH3, PH3, PCl3, PF3, CS, CH2) sandwich complexes of cyclooctatetraene: theoretical investigation

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This paper reports the molecular structure, the electronic structure, and the decomposition energies of the [M3(COT)2(L)]2+ (M = Cr, Fe, Pd, and L = H2O, CO, N2, HCN, HNC, NH3, PH3, PCl3, PF3, CS, CH2, and COT = C8H8) complexes obtained by means of DFT method using BP86 and PW91 functionals with the TZP basis set. The Pd–L bonding between the Pd3 moiety and both COT ligands is weakly sensitive to the nature of the ancillary L ligands. In accordance with the coordination modes, the COT behaves as neutral distorted ligand deviating from the planarity. The calculations showed that the various complexes are found to have a low spin ground state. The MO plots and Wiberg bond indices provide further information about the nature of the Pd–Pd bonding. The Ziegler–Rauk energy decomposition analysis scheme was employed to characterize the geometry distortion and steric interaction (electrostatic and Pauli) and orbital interaction terms in the total bonding energy of Pd complexes. The results showed that the interaction terms are governed by one third covalent and two third ionic characters, in agreement with the ΔEelstat (electrostatic) and ΔEorb (orbital) contributions, respectively, into the total attractive interaction (ΔEelstat + ΔEorb) for the studied complexes except for those of PCl3 and N2 ligands, which are almost of half covalent and half ionic characters. The σ-donation and π-backdonation amounts indicate that the CH2 is the strongest donor ligand; however, the HCN is revealed to be the weakest σ-donor and π-acceptor one. The σ-donation and π-backdonation are in perfect accord with the natural charges of the interacting fragments.

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Funding

The author 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).

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Authors and Affiliations

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

    Akila Benmachiche & Bachir Zouchoune

  2. Université Constantine 3, (25000), Constantine, Algeria

    Akila Benmachiche

  3. Laboratoire de Chimie appliquée et Technologie des Matériaux, Université Larbi Ben M’Hidi - Oum El Bouaghi, (04000), Oum El Bouaghi, Algeria

    Bachir Zouchoune

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  1. Akila Benmachiche
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Benmachiche, A., Zouchoune, B. Coordination and ligands’ effects in trinuclear [Pd3(COT)2(L)]2+ (L = H2O, CO, N2, HCN, HNC, NH3, PH3, PCl3, PF3, CS, CH2) sandwich complexes of cyclooctatetraene: theoretical investigation. Struct Chem 30, 2339–2346 (2019). https://doi.org/10.1007/s11224-019-01351-8

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