Copper(I) alkynyl clusters, [Cux+y(hfac)(x)(C=CR)(y)], with CU10-CU12 cores

Christopher W. Baxter, Timothy C. Higgs, Philip J. Bailey, Simon Parsons, Fiona McLachlan, Mary McPartlin, Peter A. Tasker

Research output: Contribution to journalArticlepeer-review

Abstract

ne facile syntheses and the structures of five new Cut alkynyl clusters, [Cu-12(hfac)(8)(C CnPr)(4)(thf)(6)].THF (1), [CU12(hfac)(8)(C CtBu)(4)] (2), [Cu-12(hfac)(8)(C CtBu)(4)] (3), [Cu-10(hfac)(6)(C CtBu)(4)(diethyl ether)]/[Cu-10(hfaC)(6)(C CtBu)(3)(C CnPr)(diethyl ether)] (4) and [Cu-10(hfac)(6)(C CtBu)4(diethyl ether)] (5) are reported, in which hfacH = 1,1,1,5,5,5-hexafluoropentan2,4-dione. The first independent molecule found in the crystals of 4 (4a) proved to be chemically identical to 5. The Cu-10 and Cu-12 cores in these clusters are based on a central "square" Cu4C4 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)-O-... 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 CtBu)] (6). When linear alkynes, CnH2n+1C CH, are used in the synthesis and non-coordinating solvents are used in the workup, further association of the Cu4C4 cores occurs and clusters with more than eighteen copper atoms are isolated.

Original languageEnglish
Pages (from-to)6166-6174
Number of pages9
JournalChemistry - A European Journal
Volume12
Issue number23
DOIs
Publication statusPublished - 7 Aug 2006

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