Expanding the tools available for direct ortho cupration--targeting lithium phosphidocuprates |
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Authors: | Harford Philip J Haywood Joanna Smith Matthew R Bhawal Benjamin N Raithby Paul R Uchiyama Masanobu Wheatley Andrew E H |
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Institution: | The University Chemical Laboratories, Lensfield Road, Cambridge CB2 1EW, UK. |
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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., (R(2)P)(2)CuLi·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(2)P)(6)Cu(4)]Li·4thf](2)1 reveals an ion-separated structure in the solid state, with solvated lithium cations countering the charge on an adamantyl dianion (Ph(2)P)(6)Cu(4)](2-). Deployment of R = Ph, X = CN in thf affords a novel network based on the dimer of Ph(2)PCu(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(2)PLi (Cy = cyclohexyl) has been reacted with CuCN in thf/toluene to yield Gilman-type lithium bis(phosphido)cuprate (Cy(2)P)(2)CuLi·2thf 3 by the exclusion of in situ generated LiCN. A polymer is noted in the solid state. |
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