Identification of the Vibrational Modes in the Far-Infrared Spectra of Ruthenium Carbonyl Clusters and the Effect of Gold Substitution

Trystan Bennett, Rohul Adnan, Jason Alvino, Vladimir Golovko, Gunther Andersson, Gregory Metha

    Research output: Contribution to journalArticle

    7 Citations (Scopus)

    Abstract

    High-quality far-IR absorption spectra for a series of ligated atomically precise clusters containing Ru3, Ru4, and AuRu3 metal cores have been observed using synchrotron radiation, the latter two for the first time. The experimental spectra are compared with predicted IR spectra obtained following complete geometric optimization of the full cluster, including all ligands, using DFT. We find strong correlations between the experimental and predicted transitions for the low-frequency, low-intensity metal core vibrations as well as the higher frequency and intensity metal-ligand vibrations. The metal core vibrational bands appear at 150 cm-1 for Ru3(CO)12, and 153 and 170 cm-1 for H 4Ru4(CO)12, while for the bimetallic Ru 3(μ-AuPPh3)(μ-Cl)(CO)10 cluster these are shifted to 177 and 299 cm-1 as a result of significant restructuring of the metal core and changes in chemical composition. The computationally predicted IR spectra also reveal the expected atomic motions giving rise to the intense peaks of metal-ligand vibrations at ca. 590 cm-1 for Ru 3, 580 cm-1 for Ru4, and 560 cm-1 for AuRu3. The obtained correlations allow an unambiguous identification of the key vibrational modes in the experimental far-IR spectra of these clusters for the first time.

    Original languageEnglish
    Pages (from-to)4340-4349
    Number of pages10
    JournalInorganic Chemistry
    Volume53
    Issue number9
    DOIs
    Publication statusPublished - 2014

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