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Issue 20, 2012
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Expanding the tools available for direct ortho cupration – targeting lithium phosphidocuprates

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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., (R2P)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. [(Ph2P)6Cu4][Li·4thf]21 reveals an ion-separated structure in the solid state, with solvated lithium cations countering the charge on an adamantyl dianion [(Ph2P)6Cu4]2−. Deployment of R = Ph, X = CN in thf affords a novel network based on the dimer of Ph2PCu(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. Cy2PLi (Cy = cyclohexyl) has been reacted with CuCN in thf/toluene to yield Gilman-type lithium bis(phosphido)cuprate (Cy2P)2CuLi·2thf 3 by the exclusion of in situ generated LiCN. A polymer is noted in the solid state.

Graphical abstract: Expanding the tools available for direct ortho cupration – targeting lithium phosphidocuprates

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Publication details

The article was received on 13 Dec 2011, accepted on 16 Mar 2012, published on 12 Apr 2012 and first published online on 12 Apr 2012


Article type: Paper
DOI: 10.1039/C2DT12415G
Citation: Dalton Trans., 2012,41, 6148-6154
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    Expanding the tools available for direct ortho cupration – targeting lithium phosphidocuprates

    P. J. Harford, J. Haywood, M. R. Smith, B. N. Bhawal, P. R. Raithby, M. Uchiyama and A. E. H. Wheatley, Dalton Trans., 2012, 41, 6148
    DOI: 10.1039/C2DT12415G

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