title: Expanding the tools available for direct ortho cupration--targeting lithium phosphidocuprates.
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.
authors.affiliation: The University Chemical Laboratories, Lensfield Road, Cambridge CB2 1EW, UK.
authors.forename: Philip J
authors.initials: PJ
authors.lastname: Harford
authors.forename: Joanna
authors.initials: J
authors.lastname: Haywood
authors.forename: Matthew R
authors.initials: MR
authors.lastname: Smith
authors.forename: Benjamin N
authors.initials: BN
authors.lastname: Bhawal
authors.forename: Paul R
authors.initials: PR
authors.lastname: Raithby
authors.forename: Masanobu
authors.initials: M
authors.lastname: Uchiyama
authors.forename: Andrew E H
authors.initials: AE
authors.lastname: Wheatley
mesh_terms: D000577:Amides / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*
chemical_list: D000577:Amides; D009942:Organometallic Compounds; D003300:Copper; D008094:Lithium