title: Structural effects in lithiocuprate chemistry: the elucidation of reactive pentametallic complexes.
abstract: TMPLi (TMP=2,2,6,6-tetramethylpiperidide) reacts with Cu(I) salts in the presence of Et2O to give the dimers [{(TMP)2Cu(X)Li2 (OEt2)}2] (X=CN, halide). In contrast, the use of DMPLi (DMP=cis-2,6-dimethylpiperidide) gives an unprecedented structural motif; [{(DMP)2CuLi(OEt2)}2LiX] (X=halide). This formulation suggests a hitherto unexplored route to the in situ formation of Gilman-type bases that are of proven reactivity in directed ortho cupration.
authors.affiliation: Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW (UK).
authors.forename: Philip J
authors.initials: PJ
authors.lastname: Harford
authors.forename: Andrew J
authors.initials: AJ
authors.lastname: Peel
authors.forename: Joseph P
authors.initials: JP
authors.lastname: Taylor
authors.forename: Shinsuke
authors.initials: S
authors.lastname: Komagawa
authors.forename: Paul R
authors.initials: PR
authors.lastname: Raithby
authors.forename: Thomas P
authors.initials: TP
authors.lastname: Robinson
authors.forename: Masanobu
authors.initials: M
authors.lastname: Uchiyama
authors.forename: Andrew E H
authors.initials: AE
authors.lastname: Wheatley
mesh_terms: D003300:Copper / Q000737:chemistry*; D008094:Lithium / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D003300:Copper; D008094:Lithium
keywords: copper; density functional calculations; directed metalation; lithium; solid-state structures