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Expanding the tools available for direct ortho cupration - Targeting lithium phosphidocuprates


Reference:

Harford, P. J., Haywood, J., Smith, M. R., Bhawal, B. N., Raithby, P. R., Uchiyama, M. and Wheatley, A. E. H., 2012. Expanding the tools available for direct ortho cupration - Targeting lithium phosphidocuprates. Dalton Transactions, 41 (20), pp. 6148-6154.

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    Official URL:

    http://dx.doi.org/10.1039/c2dt12415g

    Abstract

    Reaction of in situ generated lithium phosphides with 0.5 eq. Cu(i) is employed as a means of targeting lithium phosphidocuprates of either Gilman- or Lipshutz-type formulation - e.g., (R 2P) 2CuLi·n(LiX) (n = 0, 1). For R = Ph, X = CN in toluene followed by thf or R = Ph, X = I in thf/toluene an unexpected product results. [(Ph 2P) 6Cu 4][Li·4thf] 21 reveals an ion-separated structure in the solid state, with solvated lithium cations countering the charge on an adamantyl dianion [(Ph 2P) 6Cu 4] 2-. Deployment of R = Ph, X = CN in thf affords a novel network based on the dimer of Ph 2PCu(CN)Li·2thf 2 with trianions based on 6-membered (PCu) 3 rings acting as nodes in the supramolecular array and solvated alkali metal counter-ions completing the linkers. Cy 2PLi (Cy = cyclohexyl) has been reacted with CuCN in thf/toluene to yield Gilman-type lithium bis(phosphido)cuprate (Cy 2P) 2CuLi·2thf 3 by the exclusion of in situ generated LiCN. A polymer is noted in the solid state.

    Details

    Item Type Articles
    CreatorsHarford, P. J., Haywood, J., Smith, M. R., Bhawal, B. N., Raithby, P. R., Uchiyama, M. and Wheatley, A. E. H.
    DOI10.1039/c2dt12415g
    DepartmentsFaculty of Science > Chemistry
    RefereedYes
    StatusPublished
    ID Code30178

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