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  • Synthetic, spectroscopic and X-ray crystallographic studies on phenylcyanamidocopper(I) complexes

    Author(s)
    AINSCOUGH, EW
    BAKER, EN
    BRADER, ML
    BRODIE, AM
    INGHAM, SL
    WATERS, JM
    HANNA, JV
    HEALY, PC
    Griffith University Author(s)
    Healy, Peter C.
    Hanna, John
    Year published
    1991
    Metadata
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    Abstract
    The preparations of phenylcyanamidocopper(I) complexes of the types [Cu2(dppe)3L2]粍e2CO [dppe = 1,2-bis(diphenylphosphino)ethane, L = a phenylcyanamide ion] and [{Cu(PPh3)2L}2] are described. The crystal structures of two of the complexes, namely [Cu2(dppe)3(4-ClC6H4NCN)2]粍e2CO (4-ClC6H4NCN = 4-chlorophenylcyanamide) and [{Cu(PPh3)2(4-MeC6H4NCN)}2](4-MeC6H4NCN = 4-methylphenylcyanamide) have been determined by X-ray diffraction techniques. Crystals of [Cu2(dppe)3(4-ClC6H4NCN)2]粍e2CO are orthorhombic, space group Pbca, with a= 22.397(14), b= 18.970(7), c= 20.341(5)Šand Z= 4. The complex contains centrosymmetric dppe-bridged ...
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    The preparations of phenylcyanamidocopper(I) complexes of the types [Cu2(dppe)3L2]粍e2CO [dppe = 1,2-bis(diphenylphosphino)ethane, L = a phenylcyanamide ion] and [{Cu(PPh3)2L}2] are described. The crystal structures of two of the complexes, namely [Cu2(dppe)3(4-ClC6H4NCN)2]粍e2CO (4-ClC6H4NCN = 4-chlorophenylcyanamide) and [{Cu(PPh3)2(4-MeC6H4NCN)}2](4-MeC6H4NCN = 4-methylphenylcyanamide) have been determined by X-ray diffraction techniques. Crystals of [Cu2(dppe)3(4-ClC6H4NCN)2]粍e2CO are orthorhombic, space group Pbca, with a= 22.397(14), b= 18.970(7), c= 20.341(5)Šand Z= 4. The complex contains centrosymmetric dppe-bridged dinuclear molecules. Each copper atom has a distorted tetrahedral geometry with the cyano nitrogen from a terminally bound [4-ClC6H4NCN]- ligand [Cu-N 1.967(5)ŝ, two phosphorus atoms from a chelating dppe and one from the bridging dppe making up the co-ordination sphere. Crystals of [{Cu(PPh3)2(4-MeC6H4NCN)}2] are monoclinic, space group P21/n, with a= 15.003(2), b= 13.844(2), c= 18.711(2)Ŭ = 101.22(1)ࠡnd Z= 2. This complex is a centrosymmetric dimer with the [4-MeC6H4NCN]- ligands bridging in a 孱,3 fashion. Each copper atom has a distorted tetrahedral geometry, being bound to two PPh3 phosphorus atoms, a terminal cyano nitrogen atom from a [4-MeC6H4NCN]- ligand [Cu-N 2.045(2)ŝ and an amido nitrogen from the centrosymmetrically related [4-MeC6H4NCN]- ligand [Cu-N 2.095(2)ŝ. The v(CN) stretching vibration for the co-ordinated phenylcyanamides occurs in the 2125-2175 cm-1 range. Solid-state cross-polarisation magic-angle-spinning (CP-MAS)31P NMR spectra at 121.47 MHz for the complexes [{Cu(PPh3)2L}2](L = XC6H4NCN; X = 4-Me, 4-Cl or H) consist of two well resolved quartets of doublets arising from each of the crystallographically independent phosphorus nuclei. The doublet structure is a consequence of homonuclear phosphorus-phosphorus two-bond coupling [2J(P1-P2)= 120 Hz]. Available structural data for phenylcyanamidocopper complexes are summarised and comparison made with related pseudohalide complexes.
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    Journal Title
    Journal of the Chemical Society, Dalton Transactions
    Volume
    1991
    Issue
    5
    Publisher URI
    http://www.rsc.org/Publishing/Journals/dt/
    DOI
    https://doi.org/10.1039/DT9910001243
    Copyright Statement
    © 1991 Royal Society of Chemistry. Please refer to the journal link for access to the definitive, published version.
    Subject
    Inorganic Chemistry
    Other Chemical Sciences
    Theoretical and Computational Chemistry
    Publication URI
    http://hdl.handle.net/10072/19929
    Collection
    • Journal articles

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