By the same authors

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3-CO-ORDINATE AND 4-CO-ORDINATE COPPER(I) COMPLEXES-1/1 AND 1/2 1-CYANOGUANIDINE-COPPER(I) HALIDE ADDUCTS

Research output: Contribution to journalArticle

Author(s)

  • M J BEGLEY
  • O EISENSTEIN
  • P HUBBERSTEY
  • S JACKSON
  • C E RUSSELL
  • P H WALTON

Department/unit(s)

Publication details

JournalJOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
DatePublished - 7 Jul 1994
Issue number13
Number of pages8
Pages (from-to)1935-1942
Original languageEnglish

Abstract

The air- and moisture-stable copper(I) complexes Cu2X2-cnge and CuX.cnge.H2O (X = Cl, Br or I) have been prepared by direct reaction of CuX and 1-cyanoguanidine (cnge) in organic solvents and by reduction of aqueous solutions of CuX2 (X = Cl or Br) containing cnge with sodium sulfite. Single crystals of Cu2Cl2.cnge 1, Cu2Br2.cnge 2 and CuBr.cnge-H2O 3 were obtained from the latter route. Complexes 1 and 2 are isostructural and comprise mutually perpendicular chains of [XCu(cnge)]n and (CuX2-)n joined at a common halogen. The [XCu(cnge)]n chain, which lies in the mirror plane of the Pbcm space group, is novel. The cyanoguanidine molecule uses both its nitrile and imino nitrogen atoms to bridge the copper atoms which complete their co-ordinatively unsaturated, trigonal-planar, geometry with the common halogen. The (CuX2-)n chain is unremarkable. Complex 3 is characterised by a zigzag (CuBr)n chain and a buckled [BrCu(cnge)]n chain joined at a common copper atom; an unco-ordinated water molecule completes its structure. The [BrCu(cnge)]n chain is similar to that in 1 and 2. The main difference is the buckling which results in a dihedral angle between adjacent cnge molecules of 8.9-degrees. The (CuBr)n chain consists of bridging bromine atoms strongly bonded to one copper and weakly bonded to the other, giving a trigonal-pyramidal copper(I) co-ordination sphere. Extended-Huckel calculations have been used to examine the factors controlling the choice of a trigonal-planar over a tetrahedral structure.

    Research areas

  • LEWIS-BASE ADDUCTS, GROUP-11 METAL(I) COMPOUNDS, X = CL, CONFORMATIONAL SYSTEMATICS, STRUCTURAL CHARACTERIZATION, CRYSTAL-STRUCTURES, CHLORIDE, BR, PYRIDINE-4-CARBONITRILE, COORDINATION

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