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  • Structural and spectroscopic studies on three-coordinate complexes of copper(I) halides with tricyclohexylphosphine

    Author(s)
    Bowmaker, GA
    Boyd, SE
    Hanna, JV
    Hart, RD
    Healy, PC
    Skelton, BW
    White, AH
    Griffith University Author(s)
    Healy, Peter C.
    Year published
    2002
    Metadata
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    Abstract
    Three-coordinate 1 1 and 1 2 compounds of copper(I) halides with tricyclohexylphosphine have been synthesised and characterized by single crystal X-ray structure determinations, 63Cu NQR spectroscopy, solid state 31P CPMAS NMR spectroscopy, and low frequency vibrational spectroscopy. The 1 1 compounds crystallize as isomorphous, centrosymmetric [(PCy3)Cu(存)2Cu(PCy3)] dimers with three-coordinate (PCuX2) copper. Solid state 31P CPMAS NMR spectra show asymmetric quartets with the spectra of the chloride and bromide compounds broadened by quadrupole relaxation effects. For X = I, 1J(31P-63Cu) is 1.74 kHz with the quadrupole ...
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    Three-coordinate 1 1 and 1 2 compounds of copper(I) halides with tricyclohexylphosphine have been synthesised and characterized by single crystal X-ray structure determinations, 63Cu NQR spectroscopy, solid state 31P CPMAS NMR spectroscopy, and low frequency vibrational spectroscopy. The 1 1 compounds crystallize as isomorphous, centrosymmetric [(PCy3)Cu(存)2Cu(PCy3)] dimers with three-coordinate (PCuX2) copper. Solid state 31P CPMAS NMR spectra show asymmetric quartets with the spectra of the chloride and bromide compounds broadened by quadrupole relaxation effects. For X = I, 1J(31P-63Cu) is 1.74 kHz with the quadrupole distortion parameter, d Cu, 11.5 נ109 Hz2. Far infrared spectra of the compounds are unusually complex with groups of strong bands in the region expected for (CuX) vibrational modes (100-260 cm-1). The 1 2 compounds crystallize as [CuX(PCy3)2] monomers. The solid state 31P NMR spectra of the bromide and iodide compounds show sharp asymmetric quartets with 1J(P-Cu) 1.20 and 1.23 kHz and d Cu 8.7 and 10.3 נ109 Hz2 respectively. Relaxation effects collapse the spectrum of the chloride to a broad doublet. Room temperature 63Cu NQR frequencies for [CuX(PCy3)2] are found to be 34.5, 33.43 and 32.06 MHz for X = Cl, Br and I respectively and are of the order of 4 MHz greater than values recorded for the 1 1 complexes. Far infrared spectra of the complexes exhibit strong bands due to (CuX) vibrational modes at 253, 189 and 156 cm-1 for X = Cl, Br and I.
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    Journal Title
    J. Chem. Soc., Dalton Transactions
    Volume
    2002
    Publisher URI
    http://www.rsc.org/publishing/journals/DT/Index.asp
    DOI
    https://doi.org/10.1039/b111121n
    Copyright Statement
    © 2002 Royal Society of Chemistry. Please refer to the journal link for access to the definitive, published version.
    Subject
    Inorganic chemistry
    Theoretical and computational chemistry
    Other chemical sciences
    Publication URI
    http://hdl.handle.net/10072/7008
    Collection
    • Journal articles

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