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Electronic structure and bonding of the dinuclear metal M2(CO)10 decacarbonyls: applications of natural orbitals for chemical valence

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Abstract

The nature of the chemical metal–metal bond in M2(CO)10 (M = Mn, Re, Tc) dinuclear decacarbonyls complexes was investigated for the first time using the natural orbital chemical valence (NOCV) approach combined with the extended transition state (ETS) for energy decomposition analysis (EDA). The optimized geometries carried out at different levels of theory BP86, BLYP, BLYPD and BP86D, showed that the latter method, i.e., BP86D, led to the best agreement with X-ray experimental measurements. The BP86D/TZP results revealed that the computed covalent contribution to the metal–metal bond are 60.5%, 54.1% and 52.0% for Mn–Mn, Re–Re and Tc–Tc, respectively. The computed total interaction energies resulting from attractive terms (ΔE orb and ΔE eles), correspond well to experimental predictions, based on bond lengths and energy interaction analysis for the studied complexes.

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Acknowledgments

The authors are grateful to Pr. Agustí Lledós, Pr. Gregori Ujaque, Dr. Manuel A. Ortuno, and all the members of their group for their valuable help during the internship at the Autonomous University of Barcelona, and to Kaouther Boudjemaa for her technical assistance. The financial support of the Mentouri University of Constantine is also acknowledged.

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Authors and Affiliations

  1. Laboratoire de Physicochimie Analytique et Cristallochimie des Matériaux Organométalliques et Biomoléculaires LPACMOB, Département de Chimie, Université Frères Mentouri, 25017, Constantine, Algeria

    Rafik Menacer & Abdelhamid Mousser

  2. Centre de Recherche Scientifique et Technique en Analyses Physico-Chimiques CRAPC, BP 384, Zone Industrielle, Bou-ismail, Tipaza, RP 42004, Algeria

    Rafik Menacer

  3. Département de Chimie, Université Frères Mentouri, Route de Ain El Bey, 25017, Constantine, Algeria

    Abdelghani May

  4. URCHEMS, Département de Chimie, Université Frères Mentouri, Route de Ain El Bey, 25017, Constantine, Algeria

    Lotfi Belkhiri

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Correspondence to Lotfi Belkhiri.

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Menacer, R., May, A., Belkhiri, L. et al. Electronic structure and bonding of the dinuclear metal M2(CO)10 decacarbonyls: applications of natural orbitals for chemical valence. J Mol Model 23, 358 (2017). https://doi.org/10.1007/s00894-017-3523-5

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