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Structural diversity of homobinuclear transition metal complexes of the phenazine ligand: theoretical investigation

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Abstract

DFT/BP86 calculations have been carried out on a series of hypothetical binuclear compounds of general formula (L3M)2(C12N2H8) (M = Sc–Ni, L3 = (CO)3, (PH3)3 and Cp−, and C12N2H8 = phenazine ligand-denoted Phn). The various structures with syn and anti configurations have been investigated, in order to determine the phenazine’s coordination to first-row transition metals of various spin states with syn and anti conformations. The lowest energy structures depend on the nature of the metal, the spin state, and the molecular symmetry. This study has shown that the electronic communication between the metal centers depends on their oxidation state and the attached ligands. The tricarbonyl and the triphosphine ligands gave rise to comparable results in terms of stability order of isomers, metal-metal bond distances, and the coordination modes. Metal-metal multiple bonding has been evidenced for Sc, Ti, and V complexes to compensate the electronic deficiency. The Cr, Mn, Fe, Co, and Ni-rich metals prefer the anti conformation due to the enhancement of the metal valence electron count. The spin density values calculated for the triplet and quintet spin structures point out that the unpaired electrons are localized generally on the metal centers. The Wiberg bond indices are used to evaluate the metal-metal bonding. Furthermore, calculations using the BP86-D functional which take into account the attractive part of the van der Waals type interaction potential between atoms and molecules that are not directly connected to each other gave comparable results to those obtained by BP86 functional in terms of coordination modes, HOMO-LUMO gaps, metal-metal bond orders, and the stability order between isomers, but with slight deviation of M–C, M–N, and M–M bond distances not exceeding 3%.

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Acknowledgements

The authors are grateful to 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 the Financial support.

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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

    Noura Naili & Bachir Zouchoune

  2. Université de Skikda, Skikda, Algeria

    Noura Naili

  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. Noura Naili
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  2. Bachir Zouchoune
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Correspondence to Bachir Zouchoune.

Electronic supplementary material

ESM 1

Selected geometrical and energetic parameters calculated for [(PH3)3M]2(Phz) (M = Sc, Ti, V, Cr, Mn, Fe, and Co) models obtained by BP86 method of singlet (S = 0) and triplet (S = 1) spin states and various symmetries (Tables S1–S3) and optimized-BP86 [(PH3)3M]2(Phz) (M = Sc, Ti, V, Cr, Mn, Fe, and Co) structures of of singlet (S = 0) and triplet (S = 1) spin states for syn and anti conformations (Figs. S1–S3) (DOCX 1698 kb)

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Naili, N., Zouchoune, B. Structural diversity of homobinuclear transition metal complexes of the phenazine ligand: theoretical investigation. Struct Chem 29, 725–739 (2018). https://doi.org/10.1007/s11224-017-1064-2

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  • DOI: https://doi.org/10.1007/s11224-017-1064-2

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