Photoinduced linkage isomers in a model ruthenium nitrosyl complex: Identification and assignment of vibrational modes
Résumé
Photoinduced NO-linkage isomers were investigated in the solid state of labelled trans-[Ru(14/15 NO)(py 4)F](ClO 4) 2 complex by combined IR-spectroscopy and DFT calculations. The calculated IR-spectra show features similar to the experimental data allowing reliable assignment of the vibrational bands. The structural change from the Ru-NO (GS) to the Ru-ON (MS1) and Ru-η 2-(NO) (MS2) linkage configuration leads to the downshift of the ν(NO) and ν(Ru-(NO)) bands, and a corresponding increase of the energy of the ν(Ru-F) band. The shift of the bands corresponds to the change of the Ru-(NO) and Ru-F bond lengths: increase of the Ru-(NO) bond length leads to the decrease of the energy of the ν(Ru-(NO)) band; decrease of the Ru-F bond length leads to the increase of the energy of the ν(Ru-F) band. These observations can be extrapolated to the family of related nitrosyl complexes and therefore be used for the qualitative prediction of the Ru-(NO) and Ru-L trans-to-NO bond lengths of different linkage isomers in the framework of one complex. While the formation of linkage isomers is a reversible process, long-time irradiation sometimes induces irreversible reactions such as the release of NO. Here, we show that the photolysis of trans-[Ru(14/15 NO)(py 4)F](ClO 4) 2 in KBr pellets may lead to the release of nitrous oxide N 2 O, conceivably through the formation of a {Ru-(κ 2-ONNO)} intermediate.
Domaines
Chimie analytiqueOrigine | Fichiers produits par l'(les) auteur(s) |
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