caa a22 4500 605512523 CHVBK 20210128100656.0 cr unu---uuuuu 210128e20150401xx s 000 0 eng 10.1007/s00894-015-2623-3 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2623-3 Electronic structure of modelized vs. real carbon-chain containing organometallic dinuclear complexes: similarities and differences [Elektronische Daten] [Abdelkader Ladjarafi, Karine Costuas, Hacène Meghezzi, Jean-François Halet] DFT calculations were carried out on the homo- and hetero-bimetallic model wires [(η5-C5H5)(dpe)Fe-C≡C-C6H4-C≡C-Fe(dpe)(η5-C5H5)] (1'), [(η7-C7H7)(dpe)Mo-C≡C-C6H4-C≡C-Mo(dpe)(η7-C7H7)] (2'), and [(η5-C5H5)(dpe)Fe-C≡C-C6H4-C≡C-Mo(dpe)(η7-C7H7)] (3') used to tentatively mimic [(η5-C5Me5)(dppe)Fe-C≡C-C6H4-C≡C-Fe(dppe)(η5-C5Me5)] (1), [(η7-C7H7)(dppe)Mo-C≡C-C6H4-C≡C-Mo(dppe)(η7-C7H7)] (2), and [(η5-C5Me5)(dppe)Fe-C≡C-C6H4-C≡C-Mo(dppe)(η7-C7H7)] (3), respectively in order to analyze the similarities and the differences between models and real compounds previously theoretically and experimentally studied, with respect to their molecular structures and properties. A comparison of the metrical data computed for the models and the real systems shows some slight discrepancy between the metal-ancillary ligand distances — shorter distances are observed in the formers — but comparable metal-Cα and Cα-Cβ distances. Incidentally, distances computed for the model molecules match more closely those measured experimentally. Replacement of adppe ligand tethered to the metal centers by a dpe group does not much alter the electronic properties. Therefore, overall, data obtained for the Mo2 models 2' compare rather well with those computed for the real systems 2. Larger alteration is noticed when Cp* is substituted by Cp, even if the general trends observed for the real iron species 1 and 3 are kept overall for the iron models 1' and 3'. Indeed, the smaller electron-donor properties of Cp affect somewhat the nodal properties of the HOMOs (less metallic character) and increase the HOMO-LUMO gaps and the ionization potentials. Despite this, similarities between models and real compounds largely overtake differences. It is shown that calculations on models provide quite acceptable results. Springer-Verlag Berlin Heidelberg, 2015 Carbon-rich compounds nationallicence Density functional theory nationallicence Electronic structure nationallicence Organometallic complexes nationallicence Organometallic wires nationallicence Spin density nationallicence Ladjarafi Abdelkader Laboratory of Thermodynamics and Molecular Modeling, Faculty of Chemistry, USTHB, Algiers, Algeria aut Costuas Karine Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1, 35042, Rennes Cédex, France aut Meghezzi Hacène Laboratory of Thermodynamics and Molecular Modeling, Faculty of Chemistry, USTHB, Algiers, Algeria aut Halet Jean-François Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1, 35042, Rennes Cédex, France aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-10 1610-2940 21:4<1 2015 21 894 https://doi.org/10.1007/s00894-015-2623-3 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2623-3 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Ladjarafi Abdelkader Laboratory of Thermodynamics and Molecular Modeling, Faculty of Chemistry, USTHB, Algiers, Algeria aut NATIONALLICENCE 700 1- Costuas Karine Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1, 35042, Rennes Cédex, France aut NATIONALLICENCE 700 1- Meghezzi Hacène Laboratory of Thermodynamics and Molecular Modeling, Faculty of Chemistry, USTHB, Algiers, Algeria aut NATIONALLICENCE 700 1- Halet Jean-François Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS, Université de Rennes 1, 35042, Rennes Cédex, France aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/4(2015-04-01), 1-10 1610-2940 21:4<1 2015 21 894