title: Copper(I) alkynyl clusters, [Cu(x+y)(hfac)(x)(C[triple chemical bond]CR)(y)], with Cu(10)-Cu(12) cores.
abstract: The facile syntheses and the structures of five new Cu(I) alkynyl clusters, [Cu(12)(hfac)(8)(C[triple chemical bond]CnPr)(4)(thf)(6)]xTHF (1), [Cu(12)(hfac)(8)(C[triple chemical bond]CtBu)(4)] (2), [Cu(12)(hfac)(8)(C[triple chemical bond]CSiMe(3))(4)] (3), [Cu(10)(hfac)(6)(C[triple chemical bond]CtBu)(4)(diethyl ether)]/[Cu(10)(hfac)(6)(C[triple chemical bond]CtBu)(3)(C[triple chemical bond]CnPr)(diethyl ether)] (4) and [Cu(10)(hfac)(6)(C[triple chemical bond]CtBu)(4)(diethyl ether)] (5) are reported, in which hfacH=1,1,1,5,5,5-hexafluoropentan-2,4-dione. The first independent molecule found in the crystals of 4 (4 a) proved to be chemically identical to 5. The Cu(10) and Cu(12) cores in these clusters are based on a central "square" Cu(4)C(4) unit. Whilst the connectivities of the Cu(10) or Cu(12) units remain identical the geometries vary considerably and depend on the bulk of the alkynyl group, weak coordination of ether molecules to copper atoms in the core and CuO intramolecular contacts formed between Cu-hfac units on the periphery of the cluster. Similar intermolecular contacts and interlocking of Cu-hfac units are formed in the simple model complex [Cu(2)(hfac)(2)(HC[triple chemical bond]CtBu)] (6). When linear alkynes, C(n)H(2n+1)C[triple chemical bond]CH, are used in the synthesis and non-coordinating solvents are used in the workup, further association of the Cu(4)C(4) cores occurs and clusters with more than eighteen copper atoms are isolated.
authors.affiliation: The School of Chemistry, The University of Edinburgh, Edinburgh, Scotland, EH9 3JJ, UK.
authors.forename: Christopher W
authors.initials: CW
authors.lastname: Baxter
authors.forename: Timothy C
authors.initials: TC
authors.lastname: Higgs
authors.forename: Philip J
authors.initials: PJ
authors.lastname: Bailey
authors.forename: Simon
authors.initials: S
authors.lastname: Parsons
authors.forename: Fiona
authors.initials: F
authors.lastname: McLachlan
authors.forename: Mary
authors.initials: M
authors.lastname: McPartlin
authors.forename: Peter A
authors.initials: PA
authors.lastname: Tasker
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006845:Hydrocarbons, Fluorinated / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: C516577:1,1,1,5,5,5-hexafluoropentan-2,4-dione; D000480:Alkynes; D006845:Hydrocarbons, Fluorinated; D009942:Organometallic Compounds; D003300:Copper