Electronic structure of modelized vs. real carbon-chain containing organometallic dinuclear complexes: similarities and differences.

Abstract

DFT calculations were carried out on the homo- and hetero-bimetallic model wires [(η(5)-C5H5)(dpe)Fe-C≡C-C6H4-C≡C-Fe(dpe)(η(5)-C5H5)] (1'), [(η(7)-C7H7)(dpe)Mo-C≡C-C6H4-C≡C-Mo(dpe)(η(7)-C7H7)] (2'), and [(η(5)-C5H5)(dpe)Fe-C≡C-C6H4-C≡C-Mo(dpe)(η(7)-C7H7)] (3') used to tentatively mimic [(η(5)-C5Me5)(dppe)Fe-C≡C-C6H4-C≡C-Fe(dppe)(η(5)-C5Me5)] (1), [(η(7)-C7H7)(dppe)Mo-C≡C-C6H4-C≡C-Mo(dppe)(η(7)-C7H7)] (2), and [(η(5)-C5Me5)(dppe)Fe-C≡C-C6H4-C≡C-Mo(dppe)(η(7)-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 a dppe 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.