Terminal end-on coordination of dinitrogen versus isoelectronic CO: A comparison using the charge displacement analysis |
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Authors: | Manuel Schmitt Ingo Krossing |
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Institution: | Institut für Anorganische und Analytische Chemie and Freiburger Materialforschungszentrum (FMF), Albert-Ludwigs-Universität Freiburg, Freiburg, Germany |
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Abstract: | The metal dinitrogen bonding in a wide series of terminal end-on dinitrogen complexes is investigated with the charge displacement analysis based on natural orbitals of chemical valence (CD-NOCV). The effect of the σ donation and π backdonation on the N N bond are discussed and compared with the observations for a series of carbonyl complexes, published in 2016 by Tarantelli et al. The σ donation is relative invariant over the series of dinitrogen complexes and has no significant effect on the N N bond strength, whereas the π backdonation causes a considerable elongation of the N N bond. Some uncommon examples of weakly bound dinitrogen with blue-shifted stretching frequency compared to free N2 (ν = 2330 cm−1) are known. The dinitrogen bonding in these complexes is simulated with a point charge. Apparently, electrostatics account for the shortened N─N bond in these systems. |
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Keywords: | charge displacement analysis dinitrogen transition metal complexes |
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