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The mixed-metal carbonyl cluster anion [Ru3Ir(CO)13]– : synthesis, molecular structure, fluxionality, reactivity

Süss-Fink, Georg ; Haak, Susanne ; Ferrand, Vincent ; Stoeckli-Evans, Helen

In: Journal of the Chemical Society, Dalton Transactions, 1997, p. 3861-3865

The new cluster anion [Ru3Ir(CO)13]–1 was synthesized in high yield from [Ru3(CO)12] and [Ir(CO)4]–. The single-crystal X-ray structure analysis of the bis(triphenylphosphoranylidene)ammonium salt revealed the presence of two isomers,... More

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    Title
    • The mixed-metal carbonyl cluster anion [Ru3Ir(CO)13]– : synthesis, molecular structure, fluxionality, reactivity
    Author
    • Süss-Fink, Georg. Institut de Chimie, Université de Neuchâtel, Switzerland
    • Haak, Susanne. Institut de Chimie, Université de Neuchâtel, Switzerland
    • Ferrand, Vincent. Institut de Chimie, Université de Neuchâtel, Switzerland
    • Stoeckli-Evans, Helen. Institut de Chimie, Université de Neuchâtel, Switzerland
    Document Type
    • Postprint
    Publication Date
    • 1997
    Language
    • English
    Published in
    • Journal of the Chemical Society, Dalton Transactions, 1997, p. 3861-3865
    Other Version
    Classification
    • Chemistry
    OAI-PMH Identifier
    • oai:doc.rero.ch:20060510121304-HA
    Submission No.
    • 20060510121304-HA
    Summary
    The new cluster anion [Ru3Ir(CO)13]–1 was synthesized in high yield from [Ru3(CO)12] and [Ir(CO)4]–. The single-crystal X-ray structure analysis of the bis(triphenylphosphoranylidene)ammonium salt revealed the presence of two isomers, [Ru3Ir(CO)11(µ-CO)2]–1a and Ru3Ir(CO)9(µ-CO)4]–1b in the same crystal. Both 1a and 1b present a tetrahedral Ru3Ir framework, differing only by the number of bridging carbonyl ligands. Variable-temperature 13C NMR spectroscopic studies of 1 revealed the fluxionality of the carbonyl ligands and the interconversion of both isomers in solution. Protonation of 1 gave the neutral cluster [HRu3Ir(CO)13] 2, whereas reaction of 1 with molecular hydrogen yielded the anion [H2Ru3Ir(CO)12]–3. Either hydrogenation of 2 or protonation of 3 gave [H3Ru3Ir(CO)12] 4. The tetrahedral structure of the hydrido derivatives was confirmed by a single-crystal X-ray structure analysis of the bis(triphenylphosphoranylidene)ammonium salt of 3.