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    Syntheses of Pentanuclear Group 6 Iridium Clusters by Core Expansion of Tetranuclear Clusters with Ir(CO)2(η5-C5Me4R) (R = H, Me)

    Access Status
    Fulltext not available
    Authors
    Randles, M.
    Simpson, Peter
    Gupta, V.
    Fu, J.
    Moxey, G.
    Schwich, T.
    Criddle, A.
    Petrie, S.
    MacLellan, J.
    Batten, S.
    Stranger, R.
    Cifuentes, M.
    Humphrey, M.
    Date
    2013
    Type
    Journal Article
    
    Metadata
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    Citation
    Randles, M. and Simpson, P. and Gupta, V. and Fu, J. and Moxey, G. and Schwich, T. and Criddle, A. et al. 2013. Syntheses of Pentanuclear Group 6 Iridium Clusters by Core Expansion of Tetranuclear Clusters with Ir(CO)2(η5-C5Me4R) (R = H, Me). Inorganic Chemistry. 52 (19): pp. 11256-11268.
    Source Title
    Inorganic Chemistry
    DOI
    10.1021/ic401502f
    ISSN
    0020-1669
    School
    Nanochemistry Research Institute
    URI
    http://hdl.handle.net/20.500.11937/37358
    Collection
    • Curtin Research Publications
    Abstract

    Mixed molybdenum/tungsten tetrairidium and dimolybdenum/ditungsten triiridium clusters were prepared in high yield by cluster-core expansion of molybdenum/tungsten triiridium and dimolybdenum/ditungsten diiridium precursors, respectively, and were analyzed by a combination of spectroscopic, structural, and theoretical techniques. Tetrahedral molybdenum/tungsten iridium mixed-metal clusters undergo cluster-core expansion with iridium capping reagents to afford trigonal-bipyramidal MIr4(μ-CO)3(CO)7(η5-C5H5)(η5-L′), MoIr4(μ3-H)(μ-CO)2(μ-η1:η5-CH2C5Me4)(CO)7(η5-C5Me5) (possessing a μ-η1:η5-CH2C5Me4 ligand derived from a C−H bond activation of a C5Me5 methyl group), M2Ir3(μ-CO)3(CO)6(η5-C5H5)2(η5-L′), W2Ir3(μ-CO)4(CO)5(η5-C5H5)2(η5-C5Me4H), and Mo2Ir3(μ-CO)3(CO)6(η5-C5Me5)2 (L′ = C5Me5, C5Me4H). The spectroscopic, electrochemical, and spectroelectrochemical behavior of the clusters have been rationalized by time-dependent density functional theory.

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