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Issue 23, 2009
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Triangular tricopper(I) clusters supported by donor-substituted triazacyclohexanes

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Abstract

Triazacyclohexanes (R3TAC, 1a–i) with pyridyl or thioether functionalities (R) in the N-substituents react with three equivalents of CuX (X = Cl (2), Br (3) or I (4)) in MeCN to give the triangular tri-copper clusters [R3TAC(CuX)3] (R = 2-pyridylmethyl (2a, 3a), 5-tbutyl-2-pyridyl (3b), 2-(3-phenylpropylthio)ethyl (3c), 2-(2-ethyl-butylthio)ethyl (3d), 2-(4-heptylthio)ethyl (2e, 3e), 2-(1-heptylthio)ethyl (3f), 2-(2,4,6-trimethyl-benzylthio)ethyl (3g), 2-(o-methyl-benzylthio)ethyl (3h) and 2-(o-fluoro-benzylthio)ethyl (2i, 3i, 4i)). The thioether complexes are stable towards air and water. The bromide bridge in the clusters can be replaced by chloride (2c, e, f, i) or iodide (4c, e, f, i) by the reaction of a dichloromethane solution of the cluster with aqueous NaI or AgCl, respectively. Crystal structures of 2a, 3a, 3b, 2e, 3h and 4i show triangular halide-bridged Cu3 clusters capped by the triazacyclohexane and stabilised by the coordination of one pyridyl or thioether arm to each copper atom. DFT calculations confirm the NMR assignments and reveal the electronic structure of the copper triangle.

Graphical abstract: Triangular tricopper(i) clusters supported by donor-substituted triazacyclohexanes

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Publication details

The article was received on 30 Oct 2008, accepted on 24 Feb 2009 and first published on 02 Apr 2009


Article type: Paper
DOI: 10.1039/B819268E
Citation: Dalton Trans., 2009,0, 4556-4568
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    Triangular tricopper(I) clusters supported by donor-substituted triazacyclohexanes

    R. D. Köhn, L. Tomás Laudo, Z. Pan, F. Speiser and G. Kociok-Köhn, Dalton Trans., 2009, 0, 4556
    DOI: 10.1039/B819268E

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